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| United States Patent |
5,514,529
|
|
Mihayashi
, et al.
|
May 7, 1996
|
Silver halide color photographic light-sensitive material containing
chemically sensitized grains and pug compound
Abstract
A light-sensitive material having at least one emulsion layer containing
silver halide grains, wherein tabular grains having an average aspect
ratio of 2 or more occupy at least 50% of the total projected area of all
grains, and the material contains a compound which releases two
photographically useful groups from one molecule through a timing group
and/or a compound which releases a photographically useful group through
two timing groups.
| Inventors:
|
Mihayashi; Keiji (Minami-ashigara, JP);
Ohkawa; Atsuhiro (Minami-ashigara, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
| Appl. No.:
|
906670 |
| Filed:
|
June 30, 1992 |
Foreign Application Priority Data
| Current U.S. Class: |
430/544; 430/223; 430/505; 430/551; 430/567; 430/955; 430/957 |
| Intern'l Class: |
G03C 001/08; G03C 007/26; G03C 007/32; G03C 008/00 |
| Field of Search: |
430/544,223,567,551,505,543,549,955,957
|
References Cited
U.S. Patent Documents
| 4439520 | Mar., 1984 | Kofron et al. | 430/434.
|
| 4861701 | Aug., 1989 | Burns | 430/543.
|
| 4965180 | Oct., 1990 | Suematsu et al. | 430/518.
|
| 5118597 | Jun., 1992 | Mihayashi et al. | 430/544.
|
| 5350666 | Sep., 1994 | Motoki | 430/544.
|
| Foreign Patent Documents |
| 0282896 | Sep., 1988 | EP.
| |
| 0337370 | Oct., 1989 | EP.
| |
| 0438129 | Jul., 1991 | EP.
| |
| 60-218645 | Nov., 1985 | JP.
| |
Other References
European Search Report.
|
Primary Examiner: Bowers, Jr.; Charles L.
Assistant Examiner: Pasterczyk; J.
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak & Seas
Claims
What is claimed is:
1. A silver halide color photographic light-sensitive material comprising a
support and thereon at least one light-sensitive emulsion layer containing
a silver halide emulsion comprising tabular grains having an average
aspect ratio of 2 or more, and at least one of the emulsion layers
contains a compound represented by the formula (III), or (IV):
##STR26##
wherein A represents a coupler residue or a redox group; INH is a
developer inhibitor group; R.sub.101 and R.sub.102 each independently
represents a hydrogen, an aryl group, an alkyl group, a halogen atom, an
alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an
amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl
group, an aryloxycarbonyl group, an acylamino group, a sulfonamido group,
an alkoxycarbonylamino group, an aryloxycarbonylamino group, an ureido
group, a cyano group, or a nitro group and in formula (III) does not
contain an INH group; R.sub.103 and R.sub.104 each independently has the
same meaning as R.sub.101 and R.sub.102 ; R.sub.105 represents an
unsubstituted phenyl group, an unsubstituted primary alkyl group, a
primary alkyl group substituted with a halogen atom, an alkoxy group, an
alkylthio group, an amino group, a carbamoyl group, a sulfamoyl group, an
alkoxycarbonyl group, an acylamino group, a sulfonamido group, an
alkoxycarbonylamino group, an ureido group, a cyano group, or a nitro
group or a group represented by --CO.sub.2 CH.sub.2 CO.sub.2 R.sub.106
wherein R.sub.106 is an unsubstituted alkyl group having 3 to 6 carbon
atoms; R.sub.111, R.sub.112 and R.sub.113 each independently represents a
hydrogen atom, an alkyl group, or an aryl group; wherein at least one of
R.sub.101 to R.sub.104 is other than a hydrogen atom and any two of
R.sub.111, R.sub.112 and R.sub.113 can be divalent groups which bond
together to form a ring.
2. The light-sensitive material according to claim 1, wherein the formula
weight of the residue remaining after removing A and INH-R.sub.105 from
formula (III) is 142 to 240 and from formula (IV) is 81 to 240.
3. The light-sensitive material according to claim 1, which contains a
compound represented by the following formula (A):
Q--SM.sup.1 Formula (A)
wherein Q is a heterocyclic group directly or indirectly bonded to a group
selected from the group consisting of --SO.sub.3 M.sup.2, --COOM.sup.2,
--OH and --NR.sup.1 R.sup.2, M.sup.1 and M.sup.2 each independently
represents a hydrogen atom, an alkali metal atom, a quaternary ammonium
group, or a quaternary phosphonium group; and R.sup.1 and R.sup.2 each
independently represents a hydrogen atom, an unsubstituted alkyl group or
an alkyl group substituted with a carboxyl group.
4. The light-sensitive material according to claim 1, wherein said silver
halide emulsion is a monodispersed emulsion and contains grains having a
variation coefficient of 0.25 or less, in terms of the grain sizes.
5. The light-sensitive material according to claim 1, wherein the projected
area of hexagonal tabular silver halide grains each having two parallel
surfaces and the ratio of the longest side to the shortest side of 2 or
less, occupies 50% or more of the total projected area of all silver
halide grains contained in said silver halide emulsion.
6. The light-sensitive material according to claim 1, wherein the same
emulsion layer contains at least two emulsions of the type identical to
said silver halide emulsion, or contains said silver halide emulsion and
at least one silver halide emulsion of any other type.
7. The light-sensitive material according to claim 4, wherein the same
emulsion layer contains at least two emulsions of the type identical to
said silver halide emulsion, or contains said silver halide emulsion and
at least one silver halide emulsion of any other type.
8. The light-sensitive material according to claim 5, wherein the same
emulsion layer contains at least two emulsions of the type identical to
said silver halide emulsion, or contains said silver halide emulsion and
at least one silver halide emulsion of any other type.
9. The light-sensitive material according to claim 1, wherein at least 50%
of the grains contained in said silver halide emulsion have at least 10
dislocation lines each.
10. The light-sensitive material according to claim 1, wherein said silver
halide grains have a relative standard deviation of 30% or less in terms
of silver iodide content.
11. The light-sensitive material according to claim 1, wherein the formula
weight of the residue remaining after removing A and INH-R.sub.105 from
formula (III) is 142 to 180 and from formula (IV) is 90 to 180.
12. The light-sensitive material according to claim 1, wherein the formula
weight of the residue remaining after removing A and INH-R.sub.105 from
formula (III) is 142 to 200 and from formula (IV) is 81 to 200.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a silver halide color photographic
light-sensitive material. More particularly, it relates to a silver halide
color photographic light-sensitive material which contains a silver halide
emulsion having tabular grains and a novel, development
inhibitor-releasing compound, which excels in sensitivity, sharpness,
color reproduction, graininess and pressure resistance, and which has its
photographic properties little changed while being stored.
2. Description of the Related Art
There is a demand for a silver halide color photographic light-sensitive
material, particularly one for photographing, which has high
light-sensitivity and excels in graininess, color reproduction and
sharpness, and which has its photographic properties little changed while
being stored.
As means for improving the sharpness and color reproduction of a
light-sensitive material, a timing DIR coupler which releases a
development-inhibiting compound through two timing groups is known. DIR
couplers of this type are disclosed in, for example, JP-A-51-146828,
("JP-A" means Published Unexamined Japanese Patent Application),
JP-A-60-218645, JP-A-61-156127, JP-A-63-37346, JP-A-1-280755,
JP-A-1-219747, JP-A-2-230139, Laid-open European Patent Applications
348139, 354532, and 403019. The use of a timing DIR coupler indeed
enhances inter-layer effect or edge effect and improves sharpness and
color reproduction to some extent. However, neither the inter-layer effect
nor the edge effect can be sufficient. This is because release of the
development-inhibiting compound is one step, and its timing is
inappropriate. Further, there is a problem that light-sensitive material
containing these couplers have their photographic properties changed
greatly while being stored.
In order to provide a light-sensitive material which has high sensitivity
and excels in graininess and sharpness, it is proposed in, for example,
JP-A-58-113934, that tabular silver halide grains be used which has an
aspect ratio (i.e., the ratio of the diameter of each grain to the
thickness thereof) of 8:1 or more. The material containing such silver
halide grains is, however, dissatisfactory in terms of color reproduction,
graininess and storage stability.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a light-sensitive
material which has high light-sensitivity and excels in graininess, color
reproduction and sharpness.
A second object of the invention is to provide a light-sensitive material
which has its photographic properties little changed while being stored.
A third object of this invention is to provide a light-sensitive material
which can be manufactured at low cost and excels in image quality, by
using an emulsion having good graininess and a timing DIR coupler which
performs its function well even if used in a small amount.
A fourth object of the invention is to provide a light-sensitive material
which excels in pressure resistance, and thus has its photographic
properties little changed even if applied with a pressure.
These objects of the invention have been achieved by a silver halide color
light-sensitive material which comprises a support and at least one
light-sensitive emulsion layer formed on the support, wherein at least one
of the emulsion layers contains a silver halide emulsion comprising
tabular grains having an average aspect ratio of 2 or more, and at least
one of the emulsion layers contains a compound represented by the
following formula (I) and/or a compound represented by the following
formula (II).
##STR1##
where A is a coupler residue or a redox group, L.sub.1 and L.sub.3 are
divalent timing groups, L.sub.2 is a timing group of tri- or more valent,
PUG is a photographically useful group, j and n are independently 0, 1 or
2, m is an integer of 1 or 2, s is 2 or greater and is determined by
subtracting 1 from the valence of L.sub.2, if there are two or more
L.sub.1, L.sub.2 or L.sub.3 in the molecule, they are either identical or
different, and if there are two or more PUGs in the molecule, they are
either identical or different;
A-L.sub.4 -L.sub.5 -PUG Formula (II)
where A and PUG are of the same definition as made in conjunction with
formula (I), L.sub.4 is --OCO-- group, --OSO group, --OSO.sub.2 -- group,
--OCS-- group, --SCO-- group, --SCS-- group, or --WCR.sub.11 R.sub.12 --
group, where W is oxygen, sulfur or tertiary amino group (--NR.sub.13 --),
R.sub.11 and R.sub.12 are independently hydrogen or a substituent,
R.sub.13 is a substituent, R.sub.11, R.sub.12 and R.sub.13 are divalent
groups and capable of combining in some cases, forming a ring, L.sub.5 is
a group which releases PUG by electron transfer along a conjugated system
or a group defined by L.sub.4.
Additional objects and advantages of the invention will be set forth in the
description which follows, and in part will be obvious from the
description, or may be learned by practice of the invention. The objects
and advantages of the invention may be realized and obtained by means of
the instrumentalities and combinations particularly pointed out in the
appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The couplers represented by the formulas (I) and (II) will now be described
in detail.
As has been pointed out, A in the formula (I) is a coupler residue or a
redox group. Examples of the coupler residue are: a yellow coupler residue
(e.g., an open chain ketomethylene-type coupler residue such as
acylacetoanilide or malondianilide); a magenta coupler residue (e.g., a
coupler residue of such as 5-pyrazolone-type, pyrazolotriazole-type, or
imdazopyrazole-type); a cyan coupler residue (e.g., a coupler residue of
phenol-type, naphthol-type, or imidazole-type disclosed in Laid-open
European Patent Application 249,453, and a pyrazopyridine-type coupler
residue disclosed in Laid-open European Patent Application 304,001); and a
colorless compound forming coupler residue (e.g., a coupler residue of
indanone-type or acetophenone-type). Other examples of the coupler residue
are the heterocyclic coupler residues which are disclosed in U.S. Pat. No.
4,315,070, U.S. Pat. No. 4,183,752, U.S. Pat. No. 4,174,969, U.S. Pat. No.
3,961,959 and U.S. Pat. No. 4,171,223, and JP-A-52-82423.
If A in the formula (I) is a redox group, this is a group that can be
oxidized by an oxidized form of a developing agent. Examples of the redox
group are: hydroquinones, catechols, pyrogallols,
1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfon amidephenols,
and sulfonamidenaphthols. These groups can be those disclosed in
JP-A-61-230135, JP-A-62-251746, JP-A-61-278852, U.S. Pat. No. 3,364,022,
U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,639,417, U.S. Pat. No. 4,684,604,
and J. Org. Chem., 29,588 (1964).
Preferable examples of A are coupler residues represented by the following
formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8),
(Cp-9), (Cp-10), and (Cp-11), since these couplers have high coupling
rates.
##STR2##
In the formulas (Cp-1) to (Cp-11), the mark * extending from a coupling
position represents the position where L.sub.1 et seq. are coupled to in
the formula (I), and also the position where L.sub.4 et seq. are coupled
to in the formula (II).
When, in the formulas (Cp-1) to (Cp-11), R.sub.51, R.sub.52, R.sub.53,
R.sub.54, R.sub.55, R.sub.56, R.sub.57, R.sub.58, R.sub.59, R.sub.60,
R.sub.61, R.sub.62, R.sub.63, R.sub.64, or R.sub.65 comprises a
nondiffusing group, the total carbon number thereof is 8 to 40, preferably
10 to 30. Otherwise, these groups should preferably have a total of 15
carbon atoms or less.
R.sub.51 to R.sub.65, k, d, e, and f, shown in the formulas (Cp-1) to
(Cp-11), will be explained in detail. R.sub.41 is an aliphatic group, an
aromatic group or a heterocyclic group, and R.sub.42 is an aromatic group
or a heterocyclic group. R.sub.43, R.sub.44, and R.sub.45 are hydrogen,
aliphatic groups, aromatic groups, or heterocyclic groups.
R.sub.51 is equal to R.sub.41. R.sub.52 and R.sub.53 are equal to R.sub.42.
The notation of k is 0 or 1. R.sub.54 is equal to R.sub.41 or is R.sub.41
CON(R.sub.43)-- group, R.sub.41 R.sub.43 N-- group, R.sub.41 SO.sub.2
N(R.sub.43)-- group, R.sub.41 S-- group, R.sub.43 O-- group, R.sub.45
N(R.sub.43)CON(R.sub.44)-- group, or .tbd.C-- group. R.sub.55 is equal to
R.sub.41. R.sub.56 and R.sub.57 are equal to R.sub.43, or are R.sub.41 S--
groups, R.sub.43 O-- groups, R.sub.41 CON(R.sub.43)-- groups, or R.sub.41
SO.sub.2 N(R.sub.43)-- groups. R.sub.58 is equal to R.sub.41. R.sub.59 is
equal to R.sub.41, or it represents R.sub.41 CON(R.sub.43)-- group,
R.sub.41 OCON(R.sub.43)-- group, R.sub.41 SO.sub.2 N(R.sub.43)-- group,
R.sub.43 R.sub.44 NCON(R.sub.45)-- group, R.sub.41 O-- group, R.sub.41 S--
group, a halogen atom, or R.sub.41 R.sub.43 N-- group. The notation of "d"
is an integer from 0 to 3. If d is plural, the plural R.sub.59 groups are
substituents which are the same or different, or can be divalent groups
combining together, forming a ring such as pyridine ring or a pyrrole
ring. R.sub.60 and R.sub.61 are equal to R.sub.41. R.sub.62 is equal to
R.sub.41, or R.sub.41 OCONH-- group, R.sub.41 SO.sub.2 NH-- group,
R.sub.43 R.sub.44 NCON(R.sub.45)-- group, R.sub.43 RNSO.sub.2 (R.sub.45)--
group, R.sub.43 O-- group, R.sub.41 S-- group, a halogen atom, or R.sub.41
R.sub.43 N-- group. R.sub.63 is equal to R.sub.41, or is R.sub.43
CON(R.sub.45)-- group, R.sub.43 R.sub.44 NCO-- group, R.sub.41 SO.sub.2
N(R.sub.44)-- group, R.sub.43 R.sub.44 NSO.sub.2 --group, R.sub.41
SO.sub.2 -- group, R.sub.43 OCO-- group, R.sub.43 O--SO.sub.2 -- group, a
halogen atom, nitro, cyano, or R.sub.43 CO-- group. The notation of "e" is
an integer from 0 to 4. When R.sub.62 or R.sub.63 are plural, these groups
are either same or different. R.sub.64 and R.sub.65 are R.sub.43 R.sub.44
NCO-- groups, R.sub.41 CO-- groups, R.sub.43 R.sub.44 NSO.sub.2 --groups,
R.sub.41 OCO-- groups, R.sub.41 SO.sub.2 --groups, nitro, or cyano.
Z.sub.1 is nitrogen or .dbd.C(R.sub.66)--group, where R.sub.66 is hydrogen
or equal to R.sub.63. Z.sub.2 is sulfur or oxygen. The notation of "f" is
either 0 or 1.
The aliphatic groups, mentioned above, are aliphatic hydrocarbon group
which has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and are
saturated or unsaturated, chain or cyclic, straight-chain or branched
chain, and substituted or unsubstituted. Typical examples of the aliphatic
groups are: methyl, ethyl, propyl, isopropyl, butyl, (t)-butyl, (i)-butyl,
(t)-amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl,
1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.
The aromatic groups, also mentioned above, are those having 6 to 20 carbon
atoms, preferably substituted or unsubstituted phenyl groups or
substituted or unsubstituted naphthyl groups.
The heterocyclic groups, mentioned above, are preferably substituted or
unsubstituted 3- to 8-membered heterocyclic groups, which have 1 to 20
carbon atoms, more preferably 1 to 7 carbon atoms, and at least one hetero
atom selected from nitrogen, oxygen and sulfur. Typical examples of the
heterocyclic groups are: 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl,
2,4-dioxo-1,3-imidazolidin-5-yl, 2-benzoxazolyl, 1,2,4-triazol-3-yl or
4-pyrazolyl.
when the aliphatic hydrocarbon groups, the aromatic groups and the
heterocyclic groups have a substituent or substituents, typical examples
of the substituent are: a halogen atom, R.sub.47 O-- group, R.sub.46 S--
group, R.sub.47 CON(R.sub.48)-- group, R.sub.47 N(R.sub.48)CO-- group,
R.sub.46 OCON(R.sub.47)-- group, R.sub.46 SO.sub.2 N(R.sub.47)-- group,
R.sub.47 R.sub.48 NSO.sub.2 -- group, R.sub.46 SO.sub.2 -- group, R.sub.47
OCO-- group, R.sub.47 R.sub.48 NCON(R.sub.49)-- group, group of the same
meaning as R.sub.46, R.sub.46 COO-- group, R.sub.47 OSO.sub.2 -- group,
cyano, nitro. R.sub.46 is an aliphatic group, an aromatic group, or a
heterocyclic group. R.sub.47, R.sub.48, and R.sub.49 are aliphatic groups,
aromatic groups, heterocyclic groups, or hydrogen. The aliphatic group,
the aromatic group, and the heterocyclic group have the same meanings as
defined above.
Preferable ranges for R.sub.51 to R.sub.65, k, d, e, and f will be
described.
Preferably, R.sub.51 is an aliphatic group or an aromatic group, R.sub.52
and R.sub.55 are preferably aromatic groups, and R.sub.53 is an aromatic
group or a heterocyclic group.
In the formula (Cp-3), R.sub.54 is preferably R.sub.41 CONH-- group or
R.sub.41 R.sub.43 N-- group, R.sub.56 and R.sub.57 are desirably an
aliphatic groups, an aromatic groups, R.sub.41 O-- groups, or R.sub.41 S--
groups, and R.sub.58 is preferably an aliphatic group or an aromatic
group. In the formula (Cp-6), R.sub.59 is desirably chlorine, an aliphatic
group, or R.sub.41 CONH-- group, d is preferably 1 or 2, and R.sub.60 is
preferably an aromatic group. In the formula (Cp-7), R.sub.59 is desirably
R.sub.41 CONH--group, d is preferably 1. In the formula (Cp-8), R.sub.61
is preferably an aliphatic group or an aromatic group, and e is preferably
0 or 1, R.sub.62 is desirably R.sub.41 OCONH-- group, R.sub.41 CONH--
group or R.sub.41 SO.sub.2 NH-- group, the location of which is preferably
5-position of the naphthol ring. In the formula (Cp-9), R.sub.63 is
preferably R.sub.41 CONH-- group, R.sub.41 SO.sub.2 NH-- group, R.sub.41
R.sub.43 NSO.sub.2 -- group, R.sub.41 SO.sub.2 -- group, R.sub.41 R.sub.43
NCO-- group, nitro, or cyano, and e is preferably 1 or 2. In the formula
(Cp-10), R.sub.63 is desirably (R.sub.43).sub.2 NCO-- group, R.sub.43
OCO-- group or R.sub.43 CO-- group, and e is preferably 1 or 2. In the
formula (Cp-11), R.sub.54 is preferably an aliphatic group, an aromatic
group, or R.sub.41 CONH-- group, and f is preferably 1. A comprises
preferably a nondiffusing group or nondiffusing groups.
In the formula (I), preferable examples of L.sub.1 are the groups specified
below:
(1) Group Utilizing Cleavage Reaction of Hemiacetal
Example of this group are disclosed in, for example, U.S. Pat. No.
4,146,396, JP-A-60-249148, and JP-A-60-249149. This group is represented
by the following formula (T-1), wherein mark * indicates the position
where the group bonds to A or L.sub.1 of the compound represented by the
formula (I), and mark ** indicates the position where the group bonds to
L.sub.1 or L.sub.2 of the compound.
*--(W--CR.sub.11 (R.sub.12)).sub.t --** Formula (T-1)
In this formula, W is oxygen, sulfur, or --NR.sub.13 -- group, R.sub.11 and
R.sub.12 are hydrogen or substituents, R.sub.13 is a substituent, t is 1
or 2. If t is 2, the two --W--CR.sub.11 (R.sub.12)-- groups are either
same or different. If R.sub.11 and R.sub.12 are substituents, typical
examples of these and R.sub.13 are R.sub.15 groups, R.sub.15 CO-- group,
R.sub.15 SO.sub.2 -- group, R.sub.15 (R.sub.16)NCO-- group, and R.sub.15
(R.sub.16)NSO.sub.2 -- group, wherein R.sub.15 is an aliphatic group, an
aromatic group, or a heterocyclic group, and R.sub.16 is hydrogen, an
aliphatic group, an aromatic group, or a heterocyclic group. In some
cases, R.sub.11, R.sub.12, and R.sub.13 may be divalent groups, combining
together, forming a ring. Specific examples of the group represented in
the formula (T-1) are as follows:
##STR3##
(2) Group Causing Cleavage Reaction by Using Intramolcular Nucleophilic
Substitution Reaction
An example of this group is the timing group disclosed in U.S. Pat. No.
4,248,292. This group is represented by the following formula (T-2):
*-Nu-Link-E-** Formula (T-2)
In the formula (T-2), Nu is a nucleophilic group, e.g., oxygen or sulfur, E
is an electrophilic group which can cleave the bond at the position ** by
a nucleophilic attack of Nu, and Link is a linking group which links Nu
and E in such a steric relation that Nu and E undergo an intramolecular
nucleophilic substitution reaction. Specific examples of the group
represented by the formula (T-2) are as follows:
##STR4##
(3) Group Causing Cleavage Reaction by Using Electron Transfer Moving
along Conjugated System
Example of this group are disclosed in, for example, U.S. Pat. Nos.
4,409,323 and 4,421,845, JP-A-57-188035, JP-A-58-98728, JP-A-58-209736,
and JP-A-58-209738. This group is represented by the following formula
(T-3):
##STR5##
In the formula (T-3), marks * and **, W, R.sub.11, R.sub.12 and t are of
the same meaning as explained in connection with the formula (T-1).
However, R.sub.11 and R.sub.12 can bond together to form a benzene ring or
a heterocyclic ring. Z.sub.1 and Z.sub.2 are independently carbon or
nitrogen, and x and y are integers of 0 or 1. If Z.sub.1 is carbon, x is
1. If Z.sub.1 is nitrogen, x is 0. Z.sub.2 has the same relationship with
y as Z.sub.1 with x. In the formula (T-3), t is 1 or 2; if t is 2, the two
-- Z.sub.1 (R.sub.11).sub.x =Z.sub.2 (R.sub.12).sub.y !-- groups can
either be same or different. The --CH.sub.2 -- group, which is adjacent to
the mark **, can be substituted by an alkyl group having 1 to 6 carbon
atoms or by a phenyl group.
Specific examples of the group represented by the formula (T-3) are as
follows:
##STR6##
(4) Group Utilizing Cleavage Reaction by Hydrolysis of Ester
An example of this group is the linking group disclosed in, for example,
West German Laid-Open Patent Application 2,626,315. This group is
represented by the following formulas (T-4) and (T-5), in which the marks
and ** are of the same meaning as explained in connection with the formula
(T-1):
*--OCO--** Formula (T-4)
*--SCS--** Formula (T-5)
(5) Group Utilizing Cleavage Reaction of Iminoketal
An example of this group is the linking group disclosed in U.S. Pat. No.
4,546,073. This group is represented by the following formula (T-6):
##STR7##
In the formula (T-6), marks * and **, and W are of the same meaning as
explained in connection with the formula (T-1). R.sub.14 is equal to
R.sub.13. Specific examples of the group represented by the formula (T-6)
are as follows:
##STR8##
Preferable examples of L.sub.1 are the groups of the formulas (T-1) to
(T-5). Particularly preferable are the groups of the formulas (T-1), (T-3)
and (T-4). Preferably, j is 0 or 1.
In the formula (I), the group L.sub.2 is a timing group of 3- or more
valent. Preferable examples of L.sub.2 are the groups represented by the
following formulas (T-L.sub.1) or (T-L.sub.2):
*--W-- Z.sub.1 --(R.sub.11).sub.x =Z.sub.2 (R.sub.12).sub.y !.sub.t
--CH.sub.2 --** Formula
(T-L.sub.1)
In the formula (T-L.sub.1), W, Z.sub.1, Z.sub.2, R.sub.11, R.sub.12, x, and
y are of the same meaning as explained in connection with the formula
(T-3) and t can be 1, 2 or 3. Marks * and ** indicate the positions where
the group bonds to A-(L.sub.1).sub.j - and -(L.sub.3).sub.n -PUG shown in
the formula (I), respectively. When R.sub.11 or R.sub.12 is plural, at
least one of R.sub.11 and R.sub.12 is a substituted or unsubstituted
methylene group which bonds to -(L.sub.3).sub.n -PUG.
A preferable example of (T-L.sub.1) is one wherein W is nitrogen. An
example more preferable is one wherein W and Z.sub.2 bonds, forming a
5-membered ring. Particularly preferable is one in which W and Z.sub.2
form an imidazole ring or a pyrazole ring.
*--N--(Z.sub.3 --**).sub.2 Formula
(T-L.sub.2)
In the formula (T-L.sub.2), marks * and ** are of the same meaning as in
the formula (T-L.sub.1), Z.sub.3 is a substituted or unsubstituted
methylene group, and two Z.sub.3 groups can be either same or different,
and can bond with each other to form a ring.
Specific examples of the timing groups represented by the formulas
(T-L.sub.1) and (T-L.sub.2) are as follows. Nonetheless, the timing groups
used in the invention are not limited to these examples.
##STR9##
The specific examples of the timing groups, described above, can have a
substituent or substituents. Examples of this substituent are: an alkyl
group (e.g., methyl, ethyl, isopropyl, t-butyl, hexyl, methoxymethyl,
methoxyethyl, chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl,
carboxyethyl, dimethylaminoethyl, benzyl, or phenetyl); an aryl group
(e.g., phenyl, naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl,
2-methoxyphenyl, 2,6-dimethylphenyl, 4-carboxyphenyl, or 4-sulfophenyl); a
heterocyclic group (e.g., 2-pyridyl, 4-pyridyl, 2-furyl, 2-thienyl or
2-pyrrolyl; a halogen atom (e.g., chloro or bromo); nitro; an alkoxy group
(e.g., ethoxy, methoxy, or isopropoxy); an aryloxy group (e.g., phenoxy);
an alkylthio group (e.g., methylthio, isopropylthio, or t-butylthio); an
arylthio group (e.g., phenylthio); an amino group (e.g., amino,
dimethylamino, or diisopropyl amino); an acylamino group (e.g.,
acetylamino or benzoyl amino); a sulfonamido group (e.g.,
methanesulfonamido or benzenesulfonamido); cyano; a carboxyl group; an
alkoxycarbonyl group (e.g., methoxycarbonyl or ethoxycarbonyl); an
aryloxycarbonyl group (e.g., phenoxycarbonyl); and a carbamoyl group
(e.g., N-ethylcarbamoyl or N-phenylcarbamoyl).
Of these substituents, preferable are an alkyl group, nitro, an alkoxy
group, an alkylthio group, an amino group, an acylamino group, a
sulfonamido group, an alkoxycarbonyl group, and a carbamoyl group.
In the formula (T-L.sub.1), the --CH.sub.2 -- group, which is adjacent to
the mark **, can be substituted by an alkyl group having 1 to 6 carbon
atoms or a phenyl group.
In the formula (I), m is preferable 1.
In the formula (I), the group represented by L.sub.3 is equal to L.sub.1,
and n is 0 or 1, preferably 0.
The photographically useful group, represented by PUG in the formula (I),
is for example an development inhibitor, a dye, a fogging agent, a
developing agent, a coupler, a bleaching accelerator, or a fixing
accelerator. Examples of the photographically useful group are the group
disclosed in U.S. Pat. No. 4,248,962 (i.e., the group represented by
general formula PUG in the patent specification), the dye disclosed in
JP-A-62-49353 (i.e., the coupling split-off group released from a coupler
in the patent specification), the development inhibitor described in U.S.
Pat. No. 4,477,563, and the breaching accelerators disclosed in
JP-A-61-201247 and JP-A-2-55 (i.e., the coupling split-off groups released
from couplers in the patent specifications). In the present invention,
particularly preferable as photographically useful group is a development
inhibitor.
Preferable examples of the development inhibitor are the groups represented
by the following formulas (INH-1) to (INH-13):
##STR10##
In the formula (INH-6), R.sub.21 is hydrogen or a substituted or
unsubstituted hydrocarbon group (e.g., methyl, ethyl, propyl, or phenyl).
(INH-7)
##STR11##
In the formulas (INH-1) to (INH-13), the mark * indicates the position
where the development inhibitor bonds to L.sub.2 or L.sub.3 of the
compound represented by the formula (I), and the mark ** indicates the
position where the development inhibitor bonds to a substituent. Examples
of the substituent can be a substituted or unsubstituted aliphatic group,
an aryl group, or a heterocyclic group. These substituents preferably
comprises the group which can be decomposed in a process solution during
photographic processing.
More specifically, examples of the aliphatic group are: methyl, ethyl,
propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl,
2-methylthioethyl, benzyl, 4-methoxybenzyl, phenetyl,
1-methoxycarbonylethyl, propyloxycarbonylmethyl, methoxycarbonyl,
phenoxycarbonyl, 2-(propyloxycarbonyl) ethyl, butyloxycarbonylmethyl,
pentyloxycarbonylmethyl, 2-cyanoethyloxycarbonylmethyl,
2,2-dichloroethyloxycarbonylmethyl, 3-nitropropyloxycarbonylmethyl,
4-nitrobenzyloxycarbonylmethyl, 2,5-dioxo-3,6-dioxadecyl, and a group
represented by --CO.sub.2 CH.sub.2 CO.sub.2 R.sub.100, where R.sub.100 is
an unsubstituted alkyl group having 1 to 8 carbon atoms.
Specific examples of the aryl group are: phenyl, naphthyl,
4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methylthiophenyl,
3-methoxycarbonylphenyl, and 4-cyanoethyloxycarbonyl)-phenyl.
Specific examples of the heterocyclic group are: 4-pyridyl, 3-pyridyl,
2-pyridyl, 2-furyl, and 2-tetrahydropyranyl.
Of the development inhibitors INH exemplified above, preferable are
(INH-1), (INH-2), (INH-3), (INH-4), (INH-9) and (INH-12). Of these six
inhibitors, (INH-1), (INH-2), (INH-3) are desirable in particular.
Preferable as a substituent which bonds to INH is an aliphatic group or a
substituted or unsubstituted phenyl group.
Particularly preferred as the compound represented by the formula (I) are
the compounds which are represented by the following formulas (Ia) and
(Ib):
A-(L.sub.1)j-W- Z.sub.1 --(R.sub.11).sub.x =Z.sub.2 (R.sub.12).sub.y
!.sub.t --CH.sub.2 -PUG Formula (Ia)
A-(L.sub.1)--N--(Z.sub.3 -PUG).sub.2 Formula (Ib)
All notations used in the formulas (Ia) and (Ib) are of the same meaning as
has been explained in connection with the formulas (I), (T-L.sub.1), and
(T-L.sub.2). In the formula (Ia), j is preferably 0 or 1. In the formulas
(Ia) and (Ib), preferable as L.sub.2 is --OC(=O)-- group, and preferable
as PUG is a development inhibitor.
If the plural photographically useful groups have different functions, the
timing group is not one which utilizes intramolecular nucleophilic
substitution. The term "function of a photographically useful group" means
the function effected by a development inhibitor, a dye, a fogging agent,
a developing agent, a coupler, a bleach accelerator, or a fixing agent. It
is particularly desirable that two or more PUGs released from the same
compound be the same development inhibitors.
The compound represented by the formula (II) will now be described. In the
formula (II), A and PUG are of the same meaning as defined in conjunction
with the formula (I). L.sub.4 is --OCO-- group, --OSO-- group, --OSO.sub.2
-- group, --OCS-- group, --SCO-- group, --SCS-- group, or --WCR.sub.11
R.sub.12 -- group. W, R.sub.11, and R.sub.12 are of the same meaning as
defined in connection with the formula (T-1) which is described as an
example of L.sub.1 in the formula (I).
If L.sub.4 is --WCR.sub.11 R.sub.12 -- group, it is desirable that W be
oxygen or a tertiary amino group. More preferably, L.sub.4 is --OCH.sub.2
-- group, or L.sub.4 is the group where W and R.sub.11 or R.sub.12 form a
ring.
If L.sub.4 is a group other than --WCR.sub.11 R.sub.12 --, it is preferably
--OCO-- group, --OSO-- group, or --OSO.sub.2 -- group, of which the most
preferred is --OCO-- group.
The group represented by L.sub.5 is either a group which releases PUG by
electron transfer along a conjugated system, or a group which is defined
as L.sub.4. The group releasing PUG by electron transfer along the
conjugated system is equal to the group represented by the formula (T-3),
which has been explained in conjunction with L.sub.1 in the formula (I).
Preferable as L.sub.5 is a group which releases PUG by electron transfer
along a conjugated system. More preferable as L.sub.5 is a group which can
bond to L.sub.4 through nitrogen.
Of the compounds represented by the formula (II) are those which are
represented by the following formulas (III) and (IV):
##STR12##
In the formula (III), A is equal to A in the formula (I). R.sub.101 and
R.sub.102 are independently hydrogen or a substituent. R.sub.103 and
R.sub.104 are independently hydrogen or a substituent. INH is a group
which can inhibit development. R.sub.105 is an unsubstituted phenyl or
primary alkyl group, or a primary alkyl group substituted by a group other
than an aryl group. At least one of groups R.sub.101 to R.sub.104 is a
substituent other than hydrogen.
##STR13##
The compounds of the formula (IV) will be described in detail. In the
formula (IV), A, INH, and R.sub.105 are equal to those defined in the
formula (III), and R.sub.111, R.sub.112, and R.sub.113 are independently
hydrogen or an organic residue. Any two of R.sub.111, R.sub.112, and
R.sub.113 can be divalent groups bonding together, forming a ring.
The compound of the formula (III) will be described in more detail.
In the formula (III), A is equal to A in the formula (I), and R.sub.101 and
R.sub.102 are independently hydrogen or a substituent. Specific examples
of the substituent are: an aryl group (e.g., phenyl, naphthyl,
p-methoxyphenyl, p-hydroxyphenyl, p-nitrophenyl, or o-chlorophenyl); an
alkyl group (e.g., methyl, ethyl, isopropyl, propyl, tert-butyl,
tert-amyl, isobutyl, sec-butyl, octyl, methoxymethyl, 1-methoxyethyl, or
2-chloroethyl); a halogen atom (e.g., fluoro, chloro, bromo, or iodo); an
alkoxy group (e.g., methoxy, ethoxy, isopropyloxy, propyloxy,
tert-butyloxy, isobutyloxy, butyloxy, octyloxy, 2-methoxyethoxy,
2-chloroethoxy, nitromethyl, 2-cyanoethyl, 2-carbamoylethyl, or
2-dimethylcarbamoylethyl); an aryloxy group (e.g., phenoxy, naphthoxy, or
p-methoxyphenoxy); an alkylthio group (e.g., methylthio, ethylthio,
isopropylthio, propylthio, tert-butylthio, isobutylthio, sec-butylthio,
octylthio, or 2-methoxyethylthio); an arylthio group (e.g., phenylthio,
naphthylthio, or p-methoxyphenylthio); an amino group (e.g., amino,
methylamino, phenylamino, dimethylamino, diethylamino, diisopropylamino,
or phenylmethylamino); a carbamoyl group (e.g., carbamoyl,
methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl,
diisopropylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl,
tert-butylcarbamoyl, phenylcarbamoyl, or phenylmethylcarbamoyl); a
sulfamoyl group (e.g., sulfamoyl, methylsulfamoyl, ethylsulfamoyl,
isopropylsulfamoyl, phenylsulfamoyl, octylsulfamoyl, dimethylsulfamoyl,
diethylsulfamoyl, diisopropylsulfamoyl, dihexylsulfamoyl, or
phenylmethylsulfamoyl); an alkoxycarbonyl group (e.g., methoxycarbonyl,
propyloxycarbonyl, isopropyloxycarbonyl, tert-butyloxycarbonyl,
tert-amyloxycarbonyl, or octyloxycarbonyl); an aryloxycarbonyl group
(e.g., phenoxycarbonyl or p-methoxyphenoxycarbonyl); an acylamino group
(e.g., acetylamino, propanoylamino, pentanoylamino, N-methylacetylamino,
or benzoylamino); a sulfonamido group (e.g., methanesulfonamido,
ethanesulfonamido, pentanesulfonamido, benzenesulfonamido, or
p-toluenesulfonamido); an alkoxycarbonylamino group (e.g.,
methoxycarbonylamino, isopropyloxycarbonylamino, tert-butoxycarbonylamino,
or hexyloxycarbonylamino); an aryloxycarbonylamino group (e.g.,
phenoxycarbonylamino); an ureido group (e.g., 3-methyluriodo or
3-phenylureido); cyano, and nitro.
R.sub.101 and R.sub.102 can either be the same or different, but it is
desirable that the sum of their formula weights be less than 120.
Preferable as substituents are an alkyl group, a halogen atom, and an
alkoxy group. An alkyl group is preferred in particular.
In the formula (III), the groups represented by R.sub.103 and R.sub.104 are
independently hydrogen or an alkyl group. Examples of the alkyl group are
methyl, ethyl, isopropyl, tert-butyl, isobutyl, hexyl, and 2-methoxyethyl.
Preferable as R.sub.103 and R.sub.104 are hydrogen, methyl, and ethyl.
Hydrogen is particularly preferred.
In the formula (III), the group represented by R.sub.105 is an
unsubstituted phenyl or primary alkyl group, or a primary alkyl group
substituted by a group other than an aryl group. Examples of the alkyl
group are: ethyl, propyl, butyl, isobutyl, pentyl, isopentyl,
2-methylbutyl, hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
2-ethylbutyl, heptyl, and octyl. Examples of the group other than an aryl
group are: a halogen atom, an alkoxy group, an alkylthio group, an amino
group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an
acylamino group, a sulfonamido group, an alkoxycarbonylamino group, an
ureido group, cyano, nitro, and a group represented by --CO.sub.2 CH.sub.2
CO.sub.2 R.sub.106. Specific examples of each of these groups are all
groups exemplified as R.sub.101 and R.sub.102, except for those having
aryl groups. R.sub.106 is an unsubstituted alkyl group having 3 to 6
carbon atoms (e.g., propyl, butyl, isobutyl, pentyl, isopentyl, or hexyl).
R.sub.105 can be substituted by two or more types of substituents.
Preferable as substituents for R.sub.105 are: fluoro, chloro, an alkoxy
group, a carbamoyl group, an alkoxycarbonyl group, cyano, nitro, and
--CO.sub.2 CH.sub.2 CO.sub.2 R.sub.106. Of these, particularly preferable
are an alkoxycarbonyl group and --CO.sub.2 CH.sub.2 CO.sub.2 R.sub.106.
Preferable as R.sub.105 are: a phenyl group, an unsubstituted primary alkyl
group having 2 to 6 carbon atoms, and a primary alkyl group substituted by
the group exemplified above as preferable as a substituent for R.sub.105.
Particularly preferable is an unsubstituted primary alkyl group having 3
to 5 carbon atoms or a primary alkyl group substituted by an
alkoxycarbonyl group.
In the formula (III), the group represented by INH is a group which can
effect development inhibition. Specific examples of this group are the
inhibitors (INH-1) to (INH-13) which have been specified in connection
with the PUG shown in the formula (I). Other comments on the INH,
including preferable scope thereof, is same as that described in
connection with formula (I).
The compound represented by the formula (IV) will now be described in
greater detail.
First, the case where R.sub.111, R.sub.112, and R.sub.113 are independently
hydrogen or a monovalent organic group will be described.
If R.sub.112 and R.sub.113 are monovalent organic groups, they are
preferably alkyl groups (e.g., methyl or ethyl), or aryl groups (e.g.,
phenyl). Preferable is the case where either R.sub.112 or R.sub.113, or
both are hydrogen. Particularly preferable is the case where both
R.sub.112 and R.sub.113 are hydrogen.
R.sub.111 is an organic group. Preferable examples of this organic group
are: an alkyl group (e.g., methyl, isopropyl, butyl, isobutyl, tert-butyl,
sec-butyl, neopentyl, or hexyl); an aryl group (e.g., phenyl), an acyl
group (e.g., acetyl or benzoyl); a sulfonyl group (e.g., methanesulfonyl
or benzensulfonyl); a carbamoyl group (e.g., ethylcarbamoyl or
phenylcarbamoyl); a sulfamoyl group (e.g., ethylsulfamoyl or
phenylsulfamoyl); an alkoxycarbonyl group (e.g., ethoxycarbonyl or
butoxycarboyl); an aryloxycarbonyl group (e.g., phenoxycarbonyl or
4-methylphenoxycarbonyl); an alkoxysulfonyl group (e.g., butoxysulfonyl or
ethoxysulfonyl); an aryl oxysulfonyl group (e.g., phenoxysulfonyl or
4-methoxyphenoxysulfonyl); cyano; nitro, nitroso; a thioacyl group (e.g.,
thioacetyl or thiobenzoyl); thiocarbamoyl group (e.g.,
ethylthiocarbamoyl); an imidoyl group (e.g., N-ethylimidoyl); an amino
group (e.g., amino, dimethylamino, or methylamino); an acylamino group
(e.g., formylamino, acetylamino, or N-methylacetylamino); an alkoxy group
(e.g., methoxy or isopropyloxy); and an aryloxy group (e.g., phenoxy).
These groups can have a substituent. Examples of the substituent are those
exemplified as R.sub.111, a halogen atom (e.g., fluoro, chloro or bromo),
a carboxyl group, and a sulfo group.
Preferably, R.sub.111 has 15 or less atoms other than hydrogen atoms. More
preferable as R.sub.111 is a substituted or unsubstituted alkyl or aryl
group. Particularly preferred is a substituted or unsubstituted alkyl
group.
The case, where two of the groups represented by R.sub.111, R.sub.112, and
R.sub.113 are divalent groups bonding together, forming a ring, will now
be explained.
The ring, thus formed, is preferably a 4- to 8-membered ring, more
preferably a 4- to 6-membered ring.
Desirable as the divalent groups are: --C(=O)--N(R.sub.114)--, --SO.sub.2
--N(R.sub.114)--, --(CH.sub.2).sub.3 --, --(CH.sub.2).sub.4 --,
--(CH.sub.2).sub.5 --, --C(=O)--(CH.sub.2).sub.2 --,
--C(=O)--N(R.sub.114)--C(=O)--, --SO.sub.2 --N(R.sub.114)--C(=O)--,
--C(=O)--C(R.sub.114)(R.sub.115)--, and --(CH.sub.2).sub.2 --O--CH.sub.2
--.
In these notations, R.sub.114 and R.sub.115 are independently hydrogen, or
equal to R.sub.111 which is a monovalent organic group. R.sub.114 and
R.sub.115 can either be the same or different.
Of R.sub.111, R.sub.112, and R.sub.113, any one which is other than the
divalent group forming a ring mentioned above is hydrogen or a monovalent
organic group. Specific examples of the organic group are equal to those
exemplified as R.sub.111, R.sub.112, and R.sub.113 for the case where
R.sub.111, R.sub.112, and R.sub.113 form no rings.
If two of R.sub.111, R.sub.112, and R.sub.113 bond together, forming a
ring, it is desirable that one of R.sub.112 and R.sub.113 be hydrogen, and
the other bonds to R.sub.111, thus forming a ring, and it is more
preferable that the divalent group have their left ends bonded to the
nitrogen atom of the compound represented by the formula (I), and their
right ends bonded to the carbon atom.
Also, preferable as R.sub.111, R.sub.112, and R.sub.113 are groups which
form no rings and which are independently hydrogen or a monovalent organic
group.
In the formulas (I) and (II), each of the formula weight of the residues
which are obtained by removing two groups represented by A and PUG from
the formula (I) or (II) respectively, is preferably 64 to 240, more
preferably 70 to 200, and still more preferably 90 to 180.
Specific examples of the compounds represented by the formulas (I) to (IV)
will be presented below. Nonetheless, compounds for use in the present
invention are not limited to these examples.
Of the compounds exemplified below, those of the formula (I), in which A is
a coupler residue, are labeled with "CA," those of the formulas (II) to
(IV), in which A is a coupler residue, are labeled with "CB," and those of
the formulas (I) to (IV), in which A is a redox group, are labeled with
"SA."
##STR14##
The compounds according of this invention can be synthesized by the methods
disclosed in, for example, U.S. Pat. Nos. 4,847,383, 4,770,990, 4,684,604
and 4,886,736, JP-A-60-218645, JP-A-61-230135, JP-A-2-37070,
JP-A-2-170832, and JP-A-2-251192, or by methods similar to these.
Actual examples of synthesizing compounds will be described.
(Synthesis 1): Synthesis of Exemplified Compound (CA-1)
The compound (CA-1) was synthesized in the synthesis route 1 illustrated
below:
##STR15##
CA-1a (3.40 g) was reacted in thionyl chloride (30 ml) for 1 hour at
60.degree. C. Next, the excessive thionyl chloride was distilled out under
reduced pressure. The resultant residue was added to a dimethylformamide
solution (0.degree. C.) containing CA-1b (7.48 g) and
diisopropylethylamine (10.5 ml). The resultant solution was stirred for 1
hour. Thereafter, the solution was poured into water (500 ml), whereby
crystals were precipitated. The crystals were filtered out, thus obtaining
9.8 g of crude crystals of CA-1c. The structure of CA-1c was identified by
means of NMR method.
CA-1c (3.20 g) and CA-1d (1.38 g) were reacted for 1 hour in
1,2-dichloroethane (30 ml). Then, an ethyl acetate solution (20 ml) of
CA-1e (3.20 g) was added therein under water-cooling. Further,
diisopropylethylamine (4.5 ml) was added, and the resultant mixture was
stirred for 1 hour.
1N hydrochloric acid was added to terminate the reaction, then chloroform
(30 ml) was added to the reaction solution for diluting the same.
Thereafter, the reaction solution was water-washed three times, and the
organic layer thereof was dried over sodium sulfate. The organic solvent
was distilled out, whereby an oily substance was obtained. This substance
was refined by means of silica-gel column chromatography (ethyl
acetate-hexane=1:5), thereby obtaining 1.20 g of exemplified compound
CA-1. The structure of compound CA-1 was identified by means of NMR
method. The compound had a melting point of 133.0.degree. to 134.0.degree.
C.
(Synthesis 2): Synthesis of Exemplified Compound (CA-19)
The compound (CA-19) was synthesized in the synthesis route 2 illustrated
below:
##STR16##
CA-19a (10.7 g) and 37% formalin aqueous solution (30 ml) were reacted for
5 hours at 70.degree. C. in acetic acid (100 ml). The solvent was
distilled out. Then, the resultant residue was refined by silica-gel
column chromatography (ethyl acetate-hexane=2:1), thus obtaining 6.4 g of
CA-19b (yield: 53%).
Next, CA-19b (3.2 g) and CA-19c (2.1 g) were suspended in chloroform (40
ml). Zinc iodide (5.7 g) was added to the suspension, whereby reaction was
proceeded for 2 hours at room temperature. 1N hydrochloric acid was added,
thus terminating the reaction. The reaction solution was diluted with 40
ml of chloroform and washed twice with water. The resultant organic layer
was dried over sodium sulfate and condensed, whereby a residue was
obtained. The residue was refined by means of silica-gel column
chromatography (ethyl acetate-hexane=1:4). As a result, 4.1 g of compound
(CA-19) was obtained (yield: 25%). The structure of this compound was
identified by NMR method, mass-spectrum analysis, and element analysis.
(Synthesis 3): Synthesis of Exemplified Compound (CA-2)
The compound (CA-2) was synthesized in the synthesis route 3 shown below:
##STR17##
CB-2a (10 mmol) was suspended in chloroform (30 ml), forming a suspension.
Thionyl chloride (20 mmol) was added to the suspension. Reaction was
proceeded for 1 hour at 50.degree. C. Next, the solvent was distilled out,
obtaining a residue. The residue was added to a dimethylformamide solution
(30 ml) containing CB-2b (10 mmol) and diisopropylethylamine (20 mmol) and
was reacted for 1 hour. The reaction solution was poured into ice water
(200 ml). Then, 50 ml of chloroform was added to the solution, which was
stirred. Thereafter, the aqueous layer was removed, and the organic layer
was water-washed twice, each time with 100 ml of water. The organic layer
was dried over sodium sulfate and condensed, whereby compound CB-2c was
obtained.
Compound CB-2c, thus obtained, was dissolved in chloroform (30 ml).
Nitrophenylchlorocarbonate (10 mmol) was added to the solution, and
reaction was proceeded for 1 hour. Next, ethyl acetate solution (50 ml) of
CB-2d (10 mmol) was added to the reaction solution, and then
diisopropylethylamine (50 mmol) was added to the solution. Reaction was
proceeded for 1 hour. 1N hydrochloric acid (10 ml) was added, thereby
terminating the reaction. The reaction solution was diluted with ethyl
acetate (10 ml). The organic layer was water-washed, dried over sodium
sulfate, and condensed, thus obtaining a residue. The residue was refined
by means of silica-gel column chromatography (eluate:ethyl
acetate-hexane=1:3). As a result, 1.94 g of compound CB-2 was obtained
(yield: 23%). Compound CB-2 had a melting point of 101.5.degree. to
102.5.degree. C.
(Synthesis 4): Synthesis of Exemplified Compound (CB-3)
The compound (CB-3) was synthesized in the synthesis route 4 illustrated
below:
##STR18##
Using CB-3a as starting material, compound CB-3 was synthesized at the
yield of 31%, in the same method as compound CB-2. Compound CB-3 had a
melting point of 68.0.degree. to 69.0.degree. C.
(Synthesis 5): Synthesis of Exemplified Compound (CB-16)
The compound (CB-16) was synthesized in the route 5 illustrated below:
##STR19##
First, 200 g of (CB-16a) and 34.7 g of (CB-16b) were dissolved in ethyl
acetate (50 ml), forming a solution. Diisopropylethylamine (142 ml) was
added to the solution. The resultant solution was stirred for 4 hours, and
crystals were precipitated. The crystals were filtered out and washed with
ethyl acetate, whereby 176 g of compound (CB-16c) was obtained (yield:
75%).
Next, 53.6 g of (CB-16c) and 27.9 g of paraformaldehyde were reacted for 4
hours in a mixture of 1,2-dichloroethane (500 ml) and acetic acid (54 ml)
under refluxing. The reacted solution was cooled to room temperature,
washed with water, dried over anhydrous sodium sulfate, and condensed. A
residue thus obtained was refined by means of silica-gel column
chromatography using chloroform as eluate, whereby 23.2 g of compound
(CB-16d) was obtained (yield: 41.2%).
Then, 23.2 g of (CB-16d) and 6.78 g of (CB-16e) were dissolved in
chloroform (250 ml), thus forming a solution. To this solution, 26.88 g of
zinc iodide was added. The resultant solution was stirred for 3 hours. 1N
hydrochloric acid was added to the solution, and the reaction solution was
washed with water. The organic layer was dried over anhydrous sodium
sulfate and condensed, obtaining a residue. The residue was refined by
means of silica-gel column chromatography (ethyl acetate-hexane=1:4). As a
result, 7.0 g of compound (CB-16) was obtained (yield: 23.9%). Compound
(CB-16) had a melting point of 117.0.degree. to 118.5.degree. C.
(Synthesis 6): Synthesis of Exemplified Compound (CB-18)
The compound (CB-18) was synthesized in the same method as synthesis 5.
Compound (CB-18) had a melting point of 61.5.degree. to 63.0.degree. C.
(Synthesis 7): Synthesis of Exemplified Compound (CB-25)
The compound (CB-25) was synthesized in the same method as synthesis 2
disclosed in JP-A-60-218645. Compound (CB-25) was obtained at yield of
7%,and had a melting point of 115.degree. C.
(Synthesis 8): Synthesis of Exemplified Compound (SA-6)
The compound (SA-6) was synthesized in the synthesis route 6 shown below:
##STR20##
First, 11.6 g of SA-6a (synthesized by the same method as described in
JP-A-61-230135) was added to 30 ml of thionyl chloride under
water-cooling. Reaction was proceeded for 1 hour at 50.degree. C. in the
resultant solution. The excessive thionyl chloride was distilled out under
reduced pressure. The crystals precipitated in the solution were washed
with a small amount of ice-cooled chloroform, thereby obtaining SA-6b in
the form of crude crystal. Next, 13.1 g of SA-6b was added at 0.degree. C.
to an N,N-dimethylformamide solution (100 ml) of 7.2 g of SA-6c and 12.1 g
of triethylamine. Reaction was effected in the resultant solution for 1
hour at room temperature.
The reaction mixture was poured into an aqueous solution of 60 ml of 2N
hydrochloric acid and 300 ml of ice water. Further, 300 ml of ethyl
acetate was added to the solution. The resultant solution was stirred. The
solution was introduced into a separating funnel, thus collecting the
organic layer. The organic layer was then water-washed several times,
dried with anhydrous sodium sulfate and condensed, whereby a residue was
obtained. The residue was refined by means of silica-gel column
chromatography (ethyl acetate-hexane=1/4 to 1/1 (V/V) was used as eluate).
As a result, 3.7 g of compound SA-6 was obtained in the amorphous form.
The compound of the formula (I) and/or the compound of the formula (II) are
added to the light-sensitive material in an amount of 1.times.10.sup.-7 to
5.times.10.sup.-4 mol/m.sup.2, preferably 1.times.10.sup.-6 to
3.times.10.sup.-4 mol/m.sup.2, more preferably 5.times.10.sup.-6 to
2.times.10.sup.-4 mol/m.sup.2.
Regarding the tabular silver halide emulsion used in the present invention,
"aspect ratio" means the ratio of the diameter of the silver halide grain
to the thickness thereof. In other words, the aspect ratio of a silver
halide grain is obtained by dividing the diameter of the grain by the
thickness thereof. Here, the word "diameter" is that of a circle which has
the area equal to the projected area of the grain, which is determined by
observing the silver halide emulsion by means of a microscope or an
electron microscope.
The average aspect ratio is an average value of the aspect ratios of
individual silver halide grains. In this case, the projected areas of the
respective grains are summed in the order of the aspect ratios from the
greatest one to the lowest one, until the summed projected areas reach 50%
of the projected areas of all grains.
The tabular silver halide grains used in the silver halide emulsion of this
invention have each an aspect ratio of 2 or more, preferably 3 to 20, more
preferably 4 to 15, or still more preferably 5 to 10. The total projected
area of the tabular grains occupies 50% or more, preferably 70% or more,
more preferably 85% or more, of the total projected area of all silver
halide grains contained in the emulsion.
The use of such an emulsion serves to provide a silver halide
light-sensitive material which has an excellent sharpness, since the
light-scattering in the layer of this emulsion is far less prominent than
in the layer of a conventional emulsion. This can be easily ascertained by
the experimental method which those skilled in the art usually perform.
Although why light-scattering is less in a layer of tabular silver halide
emulsion is unclear, it is possibly because the major surface of the
grains are orientated parallel to the support surface.
It is desirable that the tabular silver halide grains have diameters of
0.02 to 20 .mu.m, preferably 0.3 to 10.0 .mu.m, more preferably 0.4 to 5.0
.mu.m, and thicknesses of 0.5 .mu.m or less. The "diameter" of a tabular
silver halide grain is the diameter of a circle having the area equal to
the projected area of the grain. The "thickness" of a tabular silver
halide grain is the distance between the two parallel surfaces which
construct the grain.
In the present invention, more preferable tabular silver halide grains are
those which have a diameter of 0.3 to 10.0 .mu.m, a thickness of 0.3 .mu.m
or less and the average aspect ratio (diameter thickness) of 5 to 10. If
the grains have a greater diameter, a greater thickness and a greater
aspect ratio, the light-sensitive material will have, in some cases,
abnormal photographic properties when it is bent, is rolled tightly, or
contacts a sharp object. Particularly preferable is an emulsion containing
silver halide grains having a diameter of 0.4 .mu.m to 5.0 .mu.m, in which
grains having an average aspect ratio of 5 or more occupy 85% or more of
the total projected area of all grains.
The tabular silver halide grains used in the invention can be silver
chloride, silver bromide, silver chlorobromide, silver bromoiodide, or
silver bromochloroiodide. Preferable are silver bromide, silver
chlorobromide, silver bromoiodide containing 15 mol % or less of silver
iodide, or silver bromochloroiodide containing 50 mol % or less of silver
chloride and 2 mol % or less of silver iodide. The compositional
distribution of mixed silver halide is uniform or localized.
The photographic emulsion for use in the present invention are described in
the report of Cugnac, Chateau; G. F. Duffin, "Photographic Emulsion
Chemistry", Focal Press, New York (1966), pp. 66-72, and A. P. H.
Trivelli, W. F. Smith, ed., "Phot. Journal," 80 (1940), p. 285. They can
easily be prepared by the methods disclosed in JP-A-58-113927,
JP-A-58-113928. and JP-A-58-127921.
The emulsion can be prepared by, for example, forming seed crystals, 40% or
more by weight of which are tabular grains, in atmosphere of relatively
high pAg and pBr of 1.3, and then growing the seed crystals while adding
silver and a halogen solution simultaneously, and while maintaining
similar pBr. It is desirable that silver and a halogen solution be added
during the growth of grains, so that no new crystal nuclei are formed.
The size of the tabular silver halide grains can be adjusted by controlling
the temperature, selecting a kind of solvent or quality thereof, and the
addition rate of silver salt and halide.
If necessary, a silver halide solvent can bee used at the time of forming
tabular silver halide grains, thereby to control the grain size, the grain
shape (diameter/thickness, etc.), the grain size distribution, and the
growth rate of grain. Preferably, the solvent is used in an amount of
10.sup.-3 to 1.0 wt % of the reaction solution. More preferably, it is
used in an amount of 10.sup.-2 to 10.sup.-1 wt % of the reaction solution.
In the present invention, when the greater the amount of the solvent is
used, the distribution of grain size may become monodispersing, and the
grain growth speed can be enhanced. There is the tendency that the grains
grow thicker as the amount of the solvent is increased.
In the present invention, the silver halide solvent can be a known one.
Examples of silver halide solvents often used are: ammonia, thioether,
thiourea, thiocyanate salt, and thiazolinethione. The use of thioether is
disclosed in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,790,387, and the like.
The use of thiourea is described in JP-A-53-82408 and JP-A-55-77737, the
use of this cyanate salt is disclosed in U.S. Pat. Nos. 2,222,264,
2,448,534, and 3,320,069. The use of thiazolinethione is disclosed in
JP-A-53-144319.
In the process of forming or physical ripening of the silver halide grains,
a salt such as cadmium slat, zinc salt, tallium salt, iridium salt, a
complex salt of any of these metals, rhodium salt, a complex salt thereof,
iron salt, or a complex salt thereof can be used together.
To form tabular silver halide grains for use in the invention, it is
recommendable that a silver salt solution (e.g., AgNO.sub.3 aqueous
solution) and a halide solution (e.g., KBr aqueous solution), both used
for accelerating the growth of the grains, be added at higher speeds, in
greater amounts, and in higher concentrations. The method of accelerating
the growth of grains is described in, for example, U.S. Pat. Nos.
1,335,925, 3,650,757, 3,672,900, and 4,242,445, JP-A-55-142329, and
JP-A-55-158124.
If necessary, the tabular silver halide grains of the invention can be
chemically sensitized by, for example, the method disclosed in H. Frieser,
ed., "Die Grundlagen der Photographischen Prozesse mir
Silber-halogeniden," Akademische Verlagsgesellschaft, 1968, pp. 675-735.
More specifically, sulfur sensitization, reduction sensitization, and
precious-metal sensitization, can be employed, either singly or in
combination. In the sulfur sensitization, use is made of a
sulfur-containing compound that can react with silver or active gelatin,
such as thiosulfate, thiourea, mercapto compound, or rhodanine. In the
reduction sensitization, use is made of a reducing substance such as
stannous salt, amine, hydrazine derivative, formamidine sulfinic acid, or
silane compound. In the precious-metal sensitization, use is made of gold
complex salt or complex salt of a metal of Group VIII (e.g., Pt, Ir, or
Pd).
Specific examples of sulfur sensitization are disclosed in U.S. Pat. Nos.
1,574,944, 2,278,947, 2,410,689, 2,728,668, and 3,656,955. Specific
examples of reduction sensitization are disclosed in U.S. Pat. Nos.
2,419,974, 2,983,609, and 4,054,458. Specific examples of precious-metal
sensitization are described in U.S. Pat. No. 2,399,083, U.S. Pat. No.
2,448,060, and British Patent 618,061.
To save silver, it is particularly recommendable that the tabular silver
halide grains of the invention be gold-sensitized or sulfur-sensitized, or
both gold-sensitized and sulfur-sensitized.
It is desirable that the tabular silver halide grains of this invention be
spectral-sensitized with, for example, methine dyes. The tabular silver
halide grains of the invention are characterized by not only the
improvement of their sharpness, but also their high spectral speed.
Examples of the dyes used are: cyanine dye, melocyanine dye, complex
cyanine dye, complex melocyanine dye, holopoler cyanine dye, hemicyanine
dye, styryl dye, and hemioxonol dye. Of these dyes, particularly useful
are cyanine dye, melocyanine dye, and complex melocyanine dye.
Examples of useful sensitizing dyes are disclosed in German Patent 929,080,
U.S. Pat. Nos. 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959,
3,672,897 and 4,025,349, British Patent 1,242,588, and JP-B-44-14030
("JP-B" means Published Examined Japanese Patent Application.)
These sensitizing dyes can be used, either singly or in combination. In
many cases, they are used in combination, for supersensitization, as is
disclosed in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052,
3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,728,
3,814,609 and 4,026,707, British Patent 1,344,281, JP-B-43-4936,
JP-B-53-12375, and JP-A-52-109925, and JP-A-52-110618.
The photographic emulsion used in the invention can contain various
compounds to prevent fogging from occurring during the manufacture,
storage or processing of the light-sensitive material, and to stabilize
the photographic properties. More precisely, compounds known as
antifoggants and stabilizing agents can be added to the emulsion. Examples
of these compounds are: azoles such as benzothiazolium salt,
nitroindazole, triazole, benzotriazole, and benzimidazole (particularly,
nitro- or halogen-substituted derivatives); heterocyclic mercapto
compounds such as mercaptothiazole, mercaptobenzothiazole,
mercaptobenzimidazole, mercaptothiadiazole, mercaptotetrazole
(particularly, 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidine;
heterocyclic mercapto compound having water-soluble group such as a
carboxyl group or a sulfo group; thioketo compounds such as
oxazolinethion; azainedines such as triazainedine, tetraazainedine
(particularly, 4-hydroxy-substituted (1, 3, 3a, 7) tetrazinedines);
benzenethiosulfonic acids; and benzensulfinic acids. Specific examples of
these compounds, and methods of using them are disclosed in, for example,
U.S. Pat. Nos. 3,954,474, 3,982,947 and 4,021,248, and JP-B-52-28660.
It is desirable that the emulsion of the invention be a monodispersed one.
The monodispersed emulsion according to this invention is an emulsion
having the grain size distribution whose variation coefficient with
respect to the grain size of silver halide is 0.25 or less. The term
"variation coefficient" is a value obtained by dividing the standard
deviation of grain size by the average grain size. The average grain size
r is:
##EQU1##
where ri is the grain size of each emulsion grain, and ni is the number of
grains.
The standard deviation S is defined as follows:
##EQU2##
The "grain size" of each grain is the equivalent-circle diameter
corresponding to the projected area which is determined from a
micro-photograph taken of the emulsion by the known method (usually by an
electron microscope), as is disclosed in T. H. James et al., "The Theory
of the Photographic Process," third ed., pp. 36-43, Macmillan Publishing
Co., Inc. (1966). As is defined in the book, the term "equivalent-circle
diameter of projected area" is the diameter of the circle whose area is
equal to the projected area of a silver halide grain. Hence, even if the
silver halide grains are not spherical (e.g., cubic, octahedral,
tetradecahedral, tabular, potato-shaped), their average size (diameter) r
and the standard deviation S thereof can be obtained.
The variation coefficient related to the silver halide grain size is
preferably 0.25 or less, more preferably 0.20 or less, and still more
preferably 0.15 or less.
Particularly preferred as the tabular silver halide emulsion of the present
invention is one containing monodispersed hexagonal tabular silver halide
grains. An example of such an emulsion is disclosed in, for example,
JP-A-63-151618.
"Hexagonal tabular silver halide grains" are characterized in that the
shape of their {1, 1, 1} face is hexagonal, having an adjacent side ratio
of 2 or less. The term "adjacent side ratio" means the length ratio of the
longest side of a hexagon to the shortest side thereof. The hexagonal
tabular silver halide grains of the invention can have slightly rounded
corners, provided they have an adjacent side ratio of 2 or less. In the
case of hexagonal tabular grains having slightly rounded corners, the
length of any side is defined as the distance between the two points of
intersection obtained by prolonging the part of the straight line of that
side and the part of the straight lines of the two adjacent sides. It is
desirable that 1/2 or more of the each side of hexagonal tabular grain,
preferably 4/5 or more of them be substantially straight. In the present
invention, the adjacent side ratio of the grains is preferably 1 to 1.5.
The hexagonal tabular silver halide emulsion of the invention comprises a
dispersion medium and silver halide grains. The total projected area of
hexagonal tabular silver halide grains occupies 50% or more, preferably
70% or more, more preferably 90% or more, of the total projected area of
all silver halide grains.
The hexagonal tabular silver halide grains of the invention can be made of
silver bromide, silver bromoiodide, silver chlorobromide, or silver
bromochloroiodide. Of these, silver bromide and silver bromoiodide are
preferred. In the case of grains made of silver bromoiodide, their silver
iodide content is preferably 0 to 30 mol %, more preferably 2 to 15 mol %,
sill more preferably 4 to 12 mol %. Silver iodide distribution in each
grain can be uniform, or different between an internal region and an outer
region thereof. Further, each grain can have a so-called "multilayered
structure", consisting of two or more layers whose silver iodide contents
is different from each others. Preferable grains are those generally known
as "internal iodide type grains," in which the outer region contains less
silver iodide than the internal region.
The hexagonal tabular silver halide emulsion can be manufactured by the
method described in U.S. Pat. No. 4,797,354.
A monodispersed hexagonal tabular silver halide emulsion is manufactured in
three steps, i.e., a step of nucleation, a step of Ostwald ripening, and a
step of growing grains. During the nucleation, pBr is maintained at 1.0 to
2.5, and nucleation is performed in supersaturated conditions for forming
many nuclei (i.e., tabular grain nuclei) each having twined faces as
parallel as possible. The supersaturated condition is obtained by
adjusting various factors, e.g., temperature, gelatin concentration,
addition rate of a silver salt aqueous solution and a halogenated alkali
aqueous solution, pBr, iodine ion content, stirring speed, pH, amount of
the silver halide solvent used, and salt concentration. During the Ostwald
ripening, all grains formed during the nucleation step, with the exception
of tabular grain nuclei, are disappeared, and the tabular grain nuclei are
made to grow. In the ripening, the temperature, pBr, pH, the gelatin
concentration, and the amount of silver halide solvent, are adjusted, in
order to form the nuclei which has good monodispersion properties. During
the grain-growing step, pBr, amount of silver ions and halogen ions to be
added are controlled, thereby enabling to obtain hexagonal tabular silver
halide grains which have a desirable aspect ratio and an appropriate size.
During the grain-growing step, the addition rate of silver ions and
halogen ions is 30 to 100% of the critical crystal growth.
In the emulsion of the invention, it is desirable that 50% of the silver
halide grains have 10 or more dislocation lines each.
Dislocation in tabular grains can be observed by a direct method disclosed
in J. F. Hamilton, Phot. Sci. Eng., 11, 57 (1967) and T. Shlozawa, J. Soc.
Phot. Sci. Jap., 35, 213(1972), in which use is made of a transmission
electron microscope at low temperatures. More specifically, silver halide
grains separated from the emulsion, not applying a pressure which is so
high as to cause dislocation in the grains, are placed on a mesh designed
for use in electron microscope observation, and are observed by the
transmission method. During the observation, the grain sample is kept
cooling in order not to suffer from damages (e.g., printouts) due to
electron beams. In this case, the thicker the grains, the more hard it is
for electron beams to pass through the grains. Hence, electron microscope
of a high-pressure type (for example, 200 KV to the grains of 0.25 .mu.m
thick) should better be employed to observe the grains clearly. The
position and the number of the dislocation in each grain, which are
observed in a direction perpendicular to the major surface of the grain,
can be known from the photograph of the grain thus obtained.
In each tabular grain of the invention, dislocation occurs in an annular
region defined by the periphery of the grain and the closed curve obtained
by connecting positions each of which is away from the center of the long
axis by x% of the distance between the center. The value for x is
preferably 10.ltoreq.x<100, more preferably 30.ltoreq.x<98, still more
preferably 50.ltoreq.x<95. The hexagonal figure formed by connecting the
points at which dislocation initiates, i.e., the figure of the closed
curve, is substantially similar to the shape of the grain, but not
perfectly similar. The line of dislocation extends from the center of the
grain toward the side, but it meanders in many cases.
Regarding to the number of dislocation in the tabular grain of the
invention, it is preferable that more than 50% by number or more of the
tabular grains contained in the silver halide emulsion of the invention
have 10 or more dislocation lines each. More preferably, 80% by number or
more of the tabular grains have 10 or more dislocation lines each. Still
more preferably, 80% by number or more of the tabular grains have 20 or
more dislocation lines each.
Also, in the case of the tabular silver halide grains preferably used in
the invention, 50% by number or more of which have 10 or more dislocation
lines each, the relative standard deviation of silver iodide content of
each grain is preferably 30% or less, more preferably 20% or less.
The silver iodide content of each emulsion grain can be measured by
analyzing the composition of the gain by means of, for example, an X-ray
micro-analyzer. The term "relative standard deviation of silver iodide
content of each grain" means the value obtained by measuring the silver
iodide contents of at least 100 grains by the X-ray micro-analyzer,
calculating the average silver iodide content of these grains and the
standard deviation of silver iodide content from the measured value, then
by dividing the calculated value of the standard deviation of silver
iodide content by the average silver iodide content, and multiplying the
resultant value by 100. A method of measuring the silver iodide content of
each emulsion grain is described in, for example, European Patent
147,848A.
When the relative standard deviation of silver iodide content is great, the
appropriate timings at which to chemically sensitive the individual grains
will be different, and it will be impossible to make the best use of the
potential properties of all emulsion grains. Also, in this case, the
relative standard deviation in terms of the number of dislocation lines
among the grains will become to be great.
The silver iodide content Yi (mol %) of each grain and the
equivalent-sphere diameter Xi (microns) have correlation in some cases,
and have no correlation in other cases. It is desirable that the content
Yi and the diameter Xi have no correlation at all.
The structure related with halogen composition of the tabular grains can be
identified by using various methods in combination. Among these methods
are: X-ray diffraction; EPMA method (also known as "XMA method; ESCA
analysis (also known as "XPS method"). In the EPMA method, silver halide
grains are scanned with electron beams, thereby to detect the composition
of the grains. In the ESCA method, X rays are applied onto grains, and the
photoelectrons emanating from the grains are spectroscopically analyzed.
In the present invention, the words "surface of a grain" means the surface
region of the grain which is about 50 angstroms deep from the surface. The
halogen composition of this region can be usually determined by means of
the ESCA method. The words "inner portion of a grain" means the region of
the grain other than the "surface" thereof.
The emulsion containing tabular grains each having dislocation lines
mentioned above can be prepared by the methods disclosed in JP-A-63-220238
and JP-A-2-310862. Preferably, the silver halide emulsion of the present
invention has a narrow grain-size distribution. It can be manufactured,
preferably by the method described in JP-A-63-151618, comprising the steps
of Nucleation-Ostwald ripening and grain growth.
The individual grains cannot have uniform silver iodide content, however,
unless the manufacturing conditions are particularly strictly controlled.
To render the silver iodide contents of the grains uniform, it is required
that the Ostwald-ripened grains have as uniform sizes and shapes as is
possible, and also that a silver nitrate aqueous solution and an alkali
halide aqueous solution be added by double-jet method at growth step,
while maintaining pAg constant at 6.0 to 10.0. To form a uniform coating
on each grain, it is desirable that the solutions being added should have
as much supersaturated as is possible. For example, the method disclosed
in U.S. Pat. No. 4,242,445 should better be employed, in which the
solutions are added which are so supersaturated that the growth rate of
the grains is 30 to 100% of the critical crystal growth rate.
The dislocation in the tabular grains of the present invention can be
controlled by forming a high-iodine phase within each grain. More
specifically, substrate grains are first prepared, then, a high-iodine
phase is formed on each substrate grain, and finally a phase containing
less iodine is formed, covering the high-iodine phase. To make the silver
iodide contents of the grains uniform, it is important to form the
high-iodine phase mentioned above under appropriate conditions.
The term "inner high-iodine phase" means a silver halide solid solution
containing iodine. Preferable as silver halide is silver iodide, silver
bromoiodide, or silver bromochloroiodide. Of these, more preferable are
silver iodide or silver bromoiodide (iodine content: 10 to 40 mol %). The
most preferable is silver iodide.
It is required that the inner high-iodine phase should not be one uniformly
deposited on the surface of the substrate grain, rather it should be
locally present on a main surface, a side surface, a ridge, or an apex of
the substrate grain. Alternatively, the inner high-iodine phase can be
selectively epitaxially orientated at such a position.
To orientate the inner high-iodine phase so, so-called conversion method
wherein an iodide salt is singly added, or epitaxial junction method of
the type disclosed in, for example, JP-A-59-133540, JP-A-58-108526 and
JP-A-59-162540 can be employed. In either method, it is effective to
select such condition as follows, in order to make the silver iodide
content of each grain uniform. That is, the iodide salt should be added to
a solution, at a pAg value of 8.5 to 10.5, more preferably 9.0 to 10.5, at
30.degree. C. to 50.degree. C., in an amount of 1 mol % or more to all
silver content used, over 30 second to 5 minutes, under sufficient
stirring.
The tabular grain of a substrate has an iodine content lower than that of
the high-iodine phase, preferably 0 to 12 mol %, more preferably 0 to 10
mol %.
The outer phase covering the high-iodine phase has an iodine content lower
than the high-iodine phase, preferably 0 to 12 mol %, more preferably 0 to
10 mol %, still more preferably 0 to 3 mol %.
It is desirable that the inner high-iodine phase exist in an annular region
with the center being identical to that of the grain, the annular region
having an inner and an outer boundaries defined as follows, along the
long-axis direction of the grain. The inner boundary is defined so that
the silver content of the grain inside the boundary corresponds to 5 mol
%, preferably 10 mol %, more preferably 20 mol % of the total silver
content of the grain, while the outer boundary is defined so that the
silver content of the grain inside the boundary corresponds to 80 mol %,
preferably 70 mol %, more preferably 60 mol % of the total silver content
of the grain.
The term "long axis direction of the grain" means the diameter direction of
each tabular grain, in contrast to the short-axis direction which extends
in the direction of the thickness of the grain.
The iodine content of the inner high-iodine phase is 5 times or more,
preferably 20 times or more, higher than the average iodine content of the
silver iodide, silver bromoiodide or silver bromochloroiodide containing
the surface layer of the grain.
The silver halide content, which is estimated as an amount of silver, of
the inner high-iodide phase is 50 mol % or less, preferably 10 mol % or
less, more preferably 5 mol % or less of the total silver content of the
grain.
The properties of silver halide grains can be controlled by using various
compounds during the precipitation of silver halide. Such compounds can be
introduced into a reaction vessel before the precipitation of silver
halide. They can be added, along with one or more salts, by the ordinary
method. Also, the properties of silver halide can be controlled by using a
compound such as a compound of copper, iridium, lead, bismuth, cadmium,
zinc, gold, and a Group VII noble metal or a calcogen compound (e.g., a
sulfur compound, a selenium compound, or a tellurium compound), during the
precipitation of silver halide, as is described in U.S. Pat. Nos.
2,448,060, 2,628,167, 3,737,313, 3,772,031, and Research Disclosure Vol.
134, 13452 (June 1975). The inner portions of the grains in a silver
halide emulsion can be reduction-sensitized during the precipitation of
silver halide, as is described in JP-B-58-1410 and Moisar et al., "Journal
of Photographic Science," Vol. 25, pp. 19-27 (1977).
In the tabular grains used in the present invention, silver halides having
different compositions may be joined by an epitaxial junction or a
compound other than a silver halide such as silver rhodanide or zinc oxide
may be joined. Such emulsion grains are disclosed in, for examples, U.S.
Pat. Nos. 4,094,684, 4,142,900 and 4,459,353, British Patent 2,038,792,
U.S. Pat. Nos. 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962 and
3,852,067, and JP-A-59-162540.
The tabular silver halide emulsion of the present invention is usually
chemically sensitized.
The chemical sensitization is performed after the silver halide emulsion
has been formed. The emulsion can be washed after it has been formed and
before it is chemically sensitized.
Examples of chemical sensitization are disclosed in Research Disclosure No.
17643 (December 1978), p. 23, and Research Disclosure No. 18716 (November
1979), p. 648, right column. The chemical sensitization can be achieved
with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, or a
combination of two or more of these sensitizers, at pAg of 5 to 10, pH of
5 to 8, and at 30.degree. to 80.degree. C.
It is desirable that the tabular silver halide emulsion of the invention be
chemically sensitized in the presence of a spectral sensitizing dye.
Methods of chemically sensitizing emulsions in the presence of a spectral
sensitizing dye are disclosed in, for example, U.S. Pat. Nos. 4,425,426
and 4,442,201, JP-A-59-9658, JP-A-61-103149, and JP-A-61-133941. Any
spectral sensitizing dye can be used if it is of the type usually employed
in silver halide light-sensitive materials. Examples of such a spectral
sensitizing dye are disclosed in Research Disclosure No. 17643, pp. 23 and
24, and Research Disclosure No. 18716, p. 648, right column to page 649,
right column. Use can be made of either only one spectral sensitizing dye,
or a mixture of two or more spectral sensitizing dyes.
The spectral sensitizing dye or dyes can be added before the chemical
sensitization (e.g., during the forming of grains, at the end of forming
of grains, or after the washing of grains), during the chemical
sensitization, or at the end of the chemical sensitization. The dye or
dyes should better added after the forming of grains and before or at the
end of the chemical sensitization.
The spectral sensitizing dye or dyes can be added in any amount desired,
which is 30 to 100% of the saturated adsorption amount, more preferably 50
to 90% thereof.
The tabular silver halide emulsion of this invention is usually spectrally
sensitized. Examples of the spectral sensitizing dye used are disclosed in
the two Research Disclosures specified above. To spectrally sensitize the
emulsion containing a spectral sensitizing dye or dyes at the time of
chemical sensitization, dye or dyes are added or not added, which are
either same or different from those contained in the emulsion.
According to the invention, only one emulsion or two or more emulsions
having different average grain sizes can be used in light-sensitive
emulsion layers. In the case where two or more emulsions are used, they
can be used in different light-sensitive layers, respectively, or in the
same light-sensitive layer in the form of a mixture. An emulsion having an
average aspect ratio falling in the range defined by this invention and an
emulsion having an average aspect ratio falling outside the range defined
by this invention can be used in combination. Alternatively, a
monodispersed emulsion suitable for use in this invention and any other
emulsion can be used in combination. Furthermore, an emulsion containing
hexagonal tabular silver halide grains, which is suitable for use in the
invention, and any other emulsion can be used in combination.
Two or more emulsions should better be used in the form of a mixture, for
the purpose of controlling gradation, graininess, and color-development
dependency. (The graininess must be controlled over the entire range of
exposure amount, from the low exposure-amount region to the high
exposure-amount region; the color-development dependency includes
time-dependency, pH-dependency and the dependency on the composition of a
development solution such as a main developing agent and sodium sulfite.)
Particular preferable as the emulsion of this invention are those which are
disclosed in JP-A-60-143332 and JP-A60-254032 and which has a relative
standard deviation of 20% or less in terms of silver iodide content
between grains contained therein.
It suffices to use the emulsion of the invention in at least one of the
light-sensitive material according to the present invention. A coating
amount of the emulsion, which is estimated as an amount of silver
contained therein, is 0.01 to 5.0 g/m.sup.2, preferably 0.10 to 3.0
g/m.sup.2, more preferably 0.30 to 2.0 g/m.sup.2.
In the present invention, it is particularly desirable that a compound of
the following formula (A) be used in order to improve the sensitivity,
graininess and readiness of desilvering of the light-sensitive material:
Q--SM.sup.1 Formula (A)
In the formula (A), Q is a heterocyclic residue directly or indirectly
bonding a group selected from the group consisting of --SO.sub.3 M.sup.2,
--COOM.sup.2, --OH and --NR.sup.1 R.sup.2. M.sup.1 and M.sup.2 are
independently hydrogen, alkali metal, quaternary ammonium, quarternary
phosphonium. R.sup.1 and R.sup.2 are hydrogen or substituted or
unsubstituted alkyl groups.
Examples of the heterocyclic residue represented by Q in the formula (A)
are: an oxazole ring, a thiazole ring, an imidazole ring, a selenazole
ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole
ring, a pentazole ring, a pyrimidine ring, a thiadia ring, a triazine
ring, a thiadiazine ring, or a ring bonded to another carbon or hetero
ring (e.g., a benzothiazole ring, a benzotriazole ring, a benzimidazole
ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, a
triazaindolizine ring, a diazaindolizine ring, or a tetraazaindolizine
ring.)
Of the mercapto heterocyclic compounds represented by the formula (A),
particularly preferable can be those represented by the following formulas
(B) and (C):
##STR21##
In the formula (B), Y and Z are independently nitrogen or CR.sup.4, where
R.sup.4 is hydrogen, a substituted or unsubstituted alkyl group, or a
substituted or unsubstituted aryl group. R.sup.3 is an organic residue
substituted by at least one group selected from the group consisting of
--SO.sub.3 M.sup.2, --COOM.sup.2, --OH and --NR.sup.1 R.sup.2. Specific
examples of R.sup.3 are: an alkyl group having 1 to 20 carbon atoms (e.g.,
methyl, ethyl, propyl, hexyl, dodecyl, or octadecyl), and an aryl group
having 6 to 20 carbon atoms (e.g., phenyl or naphthyl). L.sup.1 is a
linking group selected from the group which consists of --S--, --O--,
--N--, --CO--, --SO-- and --SO.sup.2 --. In formula (B), n is 0 or 1.
The alkyl group and the aryl group, both specified above, can be
substituted by other substituent such as a halogen atom (e.g., F, Cl, or
Br), an alkoxy group (e.g., methoxy or methoxyethoxy), an aryloxy group
(e.g., phenoxy), an alkyl group (if R.sup.2 is an aryl group), an aryl
group (if R.sup.2 is an alkyl group), an amido group (e.g., acetoamido or
benzoylamino), a carbamoyl group (e.g., an unsubstituted carbamoyl,
phenylcarbamoyl, or methylcarbamoyl), a sulfonamido group (e.g.,
methanesulfonamido or phenylsulfonamido), a sulfamoyl group (e.g., an
unsubstituted sulfamoyl, methylsulfamoyl, or phenylsulfamoyl), a sulfonyl
group (e.g., methylsulfonyl or phenylsulfonyl), a sulfinyl group (e.g.,
methylsulfinyl or phenylsulfinyl), a cyano group, an alkoxycarbonyl group
(e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl),
or a nitro group.
If there are two or more substituents for R.sup.3, such as --SO.sub.3
M.sup.2, --COOM.sup.2, --OH or --NR.sup.1 R.sup.2, they can either same or
different.
M.sup.2 is of the same meaning as has been explained in conjunction with
the formula (A).
In the formula (C), X is sulfur, oxygen, or --N(R.sup.5)--, where R.sup.5
is hydrogen, a substituted or unsubstituted alkyl group, or a substituted
or unsubstituted aryl group.
L.sup.2 is --CONR.sup.6 --, --NR.sup.6 CO--, --SO.sub.2 NR.sup.6 --,
--NR.sup.6 SO.sub.2 --, --OCO--, --COO--, --S--, NR.sup.6 --,
--CO----SO----OCOO--, --NR.sup.6 CONR.sup.7 --, --NR.sup.6 COO--,
--OCONR.sup.6 --, OR--NR.sup.6 SO.sub.2 NR.sup.7 --, where R.sup.6 and
R.sup.7 are each hydrogen, a substituted or unsubstituted alkyl group, or
a substituted or unsubstituted aryl group.
R.sup.3 and M.sup.2 are of the same meaning as has been described in
connection with the formulas (A) and (B), and n is 0 or 1.
Examples of the substituents fro the alkyl groups and aryl groups, which
are represented by R.sup.4, R.sup.5, R.sup.6, and R.sup.7, are those
exemplified as the substituent for R.sup.3.
In the formula (A), R.sup.3 is particularly preferably --SO.sub.3 M.sup.2
and --COOM.sup.2.
Examples (1) to (39) of the preferable compound represented by the formula
(A), which is used in the present invention, will be specified below:
##STR22##
The compound of the formula (A) is known, and can be synthesized by the
methods disclosed in U.S. Pat. Nos. 2,585,388 and 2,541,924,
JP-B-42-21842, JP-A-53-50169, British Patent 1,275,701, D.A. Berges et
al., "Journal of the Heterocyclic Chemistry," Vol. 15, No. 981 (1978),
"The Chemistry of Heterocyclic Chemistry Imidazole and Derivatives, Part
I", pp. 336-9, "Chemical Abstract," Vol. 58, No. 7921 (1963), p. 394, E.
Hoggarth, "Journal of Chemical Society," pp. 1160-7 (1949), S. R. Saudler,
W. Karo, "Organic Functional Group Preparation," Academic Press, pp. 312-5
(1968), M. Chamdon, et al., "Bulletin de la Societe Chimique de France,"
723 (1954), D. A. Shirley, D. W. Alley, "Journal of American Chemical
Society," 79, 4922 (1954), A. Wohl, W. Marchwald, "Berichte" (Journal of
German Chemical Society), Vol. 22, pp. 568 (1889), Journal of American
Chemical Society, 44, pp. 1502-10, U.S. Pat. No. 3,017,270, British Patent
940,169, JP-B-49-8334, JP-A-55-59463, "Advanced in Heterocyclic
Chemistry," 9, 165-209 (1968), West German Patent 27,16,707, "The
Chemistry of Heterocyclic Compounds Imidazole and Derivatives," Vol. 1, p.
384, "Organic Synthesis," IV., 569 (1963), "Berichte," 9, 465 (1976),
"Journal of American Chemical Society," 45, 2390 (1923), JP-A-50-89034,
JP-A-53-28426, JP-A-55-21007, and JP-A-40-28496.
Preferably, the compound of the formula (A) is contained in an silver
halide emulsion layer and a hydrophilic colloid layer (e.g., an
inter-layer, a surface protective layer, an yellow filter layer, an
anti-halation layer). More preferably, the compound is contained in a
silver halide emulsion layer or a layer formed adjacent thereto.
The compound is used in an amount of 1.times.10.sup.-7 to 1.times.10.sup.-3
mol/m.sup.2, preferably 5.times.10.sup.-7 to 1.times.10.sup.-4
mol/m.sup.2, more preferably 1.times.10.sup.-6 to 3.times.10.sup.-5
mol/m.sup.2.
The light-sensitive material of the present invention needs only to have at
least one of silver halide emulsion layers, i.e., a blue-sensitive layer,
a green-sensitive layer, and a red-sensitive layer, formed on a support.
The number or order of the silver halide emulsion layers and the
non-light-sensitive layers are particularly not limited. A typical example
is a silver halide photographic light-sensitive material having, on a
support, at least one light-sensitive layers comprising a plurality of
silver halide emulsion layers which are sensitive to essentially the same
color sensitivity but has different sensitivities. The light-sensitive
layers are unit light-sensitive layer sensitive to blue, green or red. In
a multilayered silver halide color photographic light-sensitive material,
the unit light-sensitive layers are generally arranged such that red-,
green-, and blue-sensitive layers are formed from a support side in the
order named. However, this order may be reversed or a layer sensitive to
one color may be sandwiched between layers sensitive to another color in
accordance with the application.
Non-light-sensitive layers such as various types of inter-layers may be
formed between the silver halide light-sensitive layers and as the
uppermost layer and the lowermost layer.
The inter-layer may contain, e.g., couplers and DIR compounds as described
in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and
JP-A-61-20038 or a color mixing inhibitor which is normally used.
As a plurality of silver halide emulsion layers constituting each unit
light-sensitive layer, a two-layered structure of high- and low-speed
emulsion layers can be preferably used as described in West German Patent
1,121,470 or British Patent 923,045. In this case, layers are preferably
arranged such that the sensitivity is sequentially decreased toward a
support, and a non-light-sensitive layer may be formed between the silver
halide emulsion layers. In addition, as described in JP-A-57-112751,
JP-A-62-200350, JP-A-62-206541, and JP-A-62-206543, layers may be arranged
such that a low-speed emulsion layer is formed remotely from a support and
a high-speed layer is formed close to the support.
More specifically, layers may be arranged from the farthest side from a
support in an order of low-speed blue-sensitive layer (BL)/high-speed
blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed
green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed
red-sensitive layer (RL), an order of BH/BL/GL/GH/RH/RL, or an order of
BH/BL/GH/GL/RL/RH.
In addition, as described in JP-B-55-34932, layers may be arranged from the
farthest side from a support in an order of blue-sensitive
layer/GH/RH/GL/RL. Furthermore, as described in JP-A-56-25738 and
JP-A-62-63936, layers may be arranged from the farthest side from a
support in an order of blue-sensitive layer/GL/RL/GH/RH.
As described in JP-B-49-15495, three layers may be arranged such that a
silver halide emulsion layer having the highest sensitivity is arranged as
an upper layer, a silver halide emulsion layer having sensitivity lower
than that of the upper layer is arranged as an inter-layer, and a silver
halide emulsion layer having sensitivity lower than that of the
inter-layer is arranged as a lower layer, i.e., three layers having
different sensitivities may be arranged such that the sensitivity is
sequentially decreased toward the support. When a layer structure is
constituted by three layers having different sensitivities, these layers
may be arranged in an order of medium-speed emulsion layer/high-speed
emulsion layer/low-speed emulsion layer from the farthest side from a
support in a layer sensitive to one color as described in JP-A-59-202464.
Also, an order of, for example, high-speed emulsion layer/low-speed
emulsion layer/medium-speed emulsion layer or low-speed emulsion
layer/medium-speed emulsion layer/high-speed emulsion layer may be
adopted. Furthermore, the arrangement can be changed as described above
even when four or more layers are formed.
To improve the color reproduction, a donor layer (CL) of interimage effects
can be arranged near to, or arranged adjacent to, a main light-sensitive
layer BL, GL or RL. The donor layer should have a spectral sensitivity
distribution which is different from that of the main light-sensitive
layer. Donor layers of this type are disclosed in U.S. Pat. No. 4,663,271,
U.S. Pat. No. 4,705,744, U.S. Pat. No. 4,707,436, JP-A-62-160448, and
JP-A-63-89850.
As described above, various layer configuration and arrangements can be
selected in accordance with the application of the light-sensitive
material.
Halide emulsions other than the silver halide emulsion of this invention
will be described.
A preferable silver halide contained in photographic emulsion layers of the
photographic light-sensitive material of the present invention is silver
bromoiodide, silver chloroiodide, or silver bromochloro iodide containing
about 30 mol % or less of silver iodide. The most preferable silver halide
is silver bromolodide or silver bromochloroiodide containing about 2 mol %
to about 10 mol % of silver iodide.
Silver halide grains contained in the photographic emulsion may have
regular crystals such as cubic, octahedral, or tetradecahedral crystals,
irregular crystals such as spherical or tabular crystals, crystals having
defects such as crystal twinning faces, or composite shapes thereof.
The silver halide may comprise fine grains having a grain size of about 0.2
.mu.m or less or large grains having a diameter of a projected surface
area of up to about 10 .mu.m, and the emulsion may be either a
polydispersed or monodispersed emulsion.
The silver halide photographic emulsion which can be used in the present
invention can be prepared by methods described in, for example, Research
Disclosure (RD) No. 17,643 (December, 1978), pp. 22 to 23, "I. Emulsion
preparation and types", RD No. 18,716 (November, 1979), page 648, and RD
No. 307,105 (November, 1989), pp. 863 to 865; P. Glafkides, "Chemie et
Phisique Photographique", Paul Montel, 1967; G. F. Duffin, "Photographic
Emulsion Chemistry", Focal Press, 1966; and V. L. Zelikman et al., "Making
and Coating Photographic Emulsion", Focal Press, 1964.
Monodispersed emulsions described in, for example, U.S. Pat. Nos. 3,574,628
and 3,655,364 and British Patent 1,413,748 are also preferred.
Also, tabular grains having an aspect ratio of about 3 or more can be used
in the present invention. The tabular grains can be easily prepared by
methods described in, e.g., Gutoff, "Photographic Science and
Engineering", Vol. 14, PP. 248 to 257 (1970); U.S. Pat. Nos. 4,434,226,
4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
The crystal structure may be uniform, may have different halogen
compositions in the interior and the surface thereof, or may be a layered
structure. Alternatively, a silver halide having a different composition
may be joined by an epitaxial junction or a compound except for a silver
halide such as silver rhodanide or zinc oxide may be joined. A mixture of
grains having various types of crystal shapes may be used.
The above emulsion may be of any of a surface latent image type in which a
latent image is mainly formed on the surface of each grain, an internal
latent image type in which a latent image is formed in the interior of
each grain, and a type in which a latent image is formed on the surface
and in the interior of each grain. However, the emulsion must be of a
negative type. When the emulsion is of an internal latent image type, it
may be a core/shell internal latent image type emulsion described in
JP-A-63-264740. A method of preparing this core/shell internal latent
image type emulsion is described in JP-A-59-133542. Although the thickness
of a shell of this emulsion changes in accordance with development or the
like, it is preferably 3 to 40 nm, and most preferably, 5 to 20 nm.
A silver halide emulsion layer is normally subjected to physical ripening,
chemical ripening, and spectral sensitization steps before it is used.
Additives for use in these steps are described in Research Disclosure Nos.
17,643, 18,716, and 307,105 and they are summarized in the following table
A.
In the light-sensitive material of the present invention, two or more types
of emulsions different in at least one characteristic of a grain size, a
grain size distribution, a halogen composition, a grain shape, and
sensitivity can be mixed in one layer.
A surface-fogged silver halide grain described in U.S. Pat. No. 4,082,553,
an internally fogged silver halide grain described in U.S. Pat. No.
4,626,498 or JP-A-59-214852, and colloidal silver can be preferably used
in a light-sensitive silver halide emulsion layer and/or a substantially
non-light-sensitive hydrophilic colloid layer. The internally fogged or
surface-fogged silver halide grains are silver halide grains which can be
uniformly (non-imagewise) developed in either a non-exposed portion or an
exposed portion of the light-sensitive material. A method of preparing the
internally fogged or surface-fogged silver halide grain is described in
U.S. Pat. No. 4,626,498 or JP-A-59-214852.
A silver halide which forms the core of an internally fogged core/shell
type silver halide grain may have the same halogen composition as or a
different halogen composition from that of the other portion. Examples of
the internally-fogged or surface-fogged silver halide are silver chloride,
silver chlorobromide, silver bromoiodide, and silver bromochloroiodide.
Although the grain size of these fogged silver halide grains is not
particularly limited, an average grain size is 0.01 to 0.75 .mu.m, and
most preferably, 0.05 to 0.6 .mu.m. The grain shape is also not
particularly limited but may be a regular grain shape. Although the
emulsion may be a polydispersed emulsion, it is preferably a
mono-dispersed emulsion (in which at least 95% in weight or number of
silver halide grains have a grain size falling within the range of 40% of
an average grain size).
In the present invention, a non-light-sensitive fine grain silver halide is
preferably used. The non-light-sensitive fine grain silver halide means
silver halide fine grains not sensitive upon imagewise exposure for
obtaining a dye image and essentially not developed in development. The
non-light-sensitive fine grain silver halide is preferably not fogged
beforehand.
The fine grain silver halide contains 0 to 100 mol % of silver bromide and
may contain silver chloride and/or silver iodide as needed. Preferably,
the fine grain silver halide contains 0.5 to 10 mol % of silver iodide.
An average grain size (an average value of equivalent-circle diameters of
projected surface areas) of the fine grain silver halide is preferably
0.01 to 0.5 .mu.m, and more preferably, 0.02 to 0.2 .mu.m.
The fine grain silver halide can be prepared by a method similar to a
method of preparing normal light-sensitive material silver halide. In this
preparation, the surface of a silver halide grain need not be subjected to
either optical sensitization or spectral sensitization. However, before
the silver halide grains are added to a coating solution, a known
stabilizer such as a triazole compound, an azaindene compound, a
benzothiazolium compound, a mercapto compound, or a zinc compound is
preferably added. This fine grain silver halide grain containing layer
preferably contains a colloidal silver.
A coating silver amount of the light-sensitive material of the present
invention is preferably 6.0 g/m.sup.2 or less, and most preferably, 4.5
g/m.sup.2 or less.
Known photographic additives usable in the present invention are also
described in the above three RDs, and they are summarized in the following
Table A:
TABLE A
______________________________________
Additives RD17643 RD18716 RD307105
______________________________________
1. Chemical page 23 page 648, right
page 866
sensitizers column
2. Sensitivity page 648, right
increasing column
agents
3. Spectral pp. 23-24 page 648, right
pp. 866-868
sensitizers, column to page
super 649, right column
sensitizers
4. Brighteners
page 24 page 647, right
page 868
column
5. Antifoggants
pp. 24-25 page 649. right
pp. 868-870
and column
stabilizers
6. Light absorb-
pp. 25-26 page 649, right
page 873
ent. filter column to page
dye. ultra- 650. left column
violet
absorbents
7. Stain page 25, page 650. left to
page 872
preventing right column
right columns
agents
8. Dye image page 25 page 650, left
page 872
stabilizer column
9. Hardening page 26 page 651. left
pp. 874-875
agents column
10. Binder page 26 page 651. left
pp. 873-874
column
11. Plasticizers.
page 27 page 650, right
page 876
lubricants column
12. Coating aids.
pp. 26-27 page 650, right
pp. 875-876
surface active column
agents
13. Antistatic page 27 page 650, right
pp. 876-877
agents column
14. Matting agent page 650, right
pp. 878-879
column
______________________________________
In order to prevent degradation in photographic properties caused by
formaldehyde gas, a compound described in U.S. Pat. No. 4,411,987 or U.S.
Pat. No. 4,435,503, which can react with formaldehyde and fix the same, is
preferably added to the light-sensitive material.
The light-sensitive material of the present invention preferably contains
mercapto compounds described in U.S. Pat. Nos. 4,740,454 and 4,788,132,
JP-A-62-18539, and JP-A-1-283551.
The light-sensitive material of the present invention preferably contains
compounds for releasing a fogging agent, a development accelerator, a
silver halide solvent, or precursors thereof described in JP-A-1-106052
regardless of a developed silver amount produced by the development.
The light-sensitive material of the present invention preferably contains
dyes dispersed by methods described in WO 88/04794 and JP-A-1-502912 or
dyes described in European Patent 317,308A, U.S. Pat. No. 4,420,555, and
JP-A-1-259358.
Various color couplers can be used in the present invention, and specific
examples of these couplers are described in patents described in
above-mentioned Research Disclosure (RD), No. 17643, VII-C to VII-G and RD
No. 307105, VII-C to VII-G.
Preferable examples of a yellow coupler are described in, e.g., U.S. Pat.
Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961,
JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Pat. Nos.
3,973,968, 4,314,023, and 4,511,649, and EP 249,473A.
Examples of a magenta coupler are preferably 5-pyrazolone and pyrazoloazole
compounds, and more preferably, the compounds described in, e.g., U.S.
Pat. Nos. 4,310,619 and 4,351,897, European Patent 73,636, U.S. Pat. Nos.
3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659,
JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, U.S.
Pat. Nos. 4,500,630, 4,540,654, and 4,556,630, and WO 88/04795.
Examples of a cyan coupler are phenol and naphthol couplers. Of these,
preferable are those described in, e.g., U.S. Pat. Nos. 4,052,212,
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German
Laid-open Patent Application 3,329,729, European Patents 121,365A and
249,453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559,
4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658. Also,
the pyrazoloazole-series couplers disclosed in JP-A-64-553, JP-A-64-554,
JP-A-64-555 and JP-A-64-556, and imidazole-series couplers disclosed in
U.S. Pat. No. 4,818,672 can be used as cyan coupler in the present
invention.
Typical examples of a polymerized dye-forming coupler are described in U.S.
Pat. Nos. 3,451,820, 4,080,221, 4,367,282, 4,409,320, and 4,576,910,
British Patent 2,102,137, and EP 341,188A.
Preferable examples of a coupler capable of forming colored dyes having
proper diffusibility are those described in U.S. Pat. No. 4,366,237,
British Patent 2,125,570, EP 96,570, and West German Laid-open Patent
Application No. 3,234,533.
Preferable examples of a colored coupler for correcting additional,
undesirable absorption of a colored dye are those described in Research
Disclosure No. 17643, VII-G, No. 307105 VII-G, U.S. Pat. No. 4,163,670,
JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent
1,146,368. A coupler for correcting unnecessary absorption of a colored
dye by a fluorescent dye released upon coupling described in U.S. Pat. No.
4,774,181 or a coupler having a dye precursor group which can react with a
developing agent to form a dye as a split-off group described in U.S. Pat.
No. 4,777,120 may be preferably used.
Compounds releasing a photographically useful residue upon coupling are
preferably used in the present invention. DIR couplers, i.e., couplers
releasing a development inhibitor are described in the patents cited in
the above-described RD No. 17643, VII-F, RD No. 307105, VII-F,
JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346,
JP-A-63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 in addition to
the compounds represented by the formula (I) and (II) of the present
invention.
Research Disclosures Nos. 11449 and 24241, and JP-A-61-201247, for example,
disclose couplers which release breaching accelerator. These couplers
effectively serve to shorten the time of any process that involves
breaching. They are effective, particularly when added to light-sensitive
material containing tabular silver halide grains. Preferable examples of a
coupler for imagewise releasing a nucleating agent or a development
accelerator are described in British Patents 2,097,140 and 2,131,188,
JP-A-59-157638, and JP-A-59-170840. In addition, compounds for releasing a
fogging agent, a development accelerator, or a silver halide solvent upon
redox reaction with an oxidized form of a developing agent, described in
JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687, can also
be preferably used.
Examples of a coupler which can be used in the light-sensitive material of
the present invention are competing couplers described in, e.g., U.S. Pat.
No. 4,130,427; poly-equivalent couplers described in, e.g., U.S. Pat. Nos.
4,283,472, 4,338,393, and 4,310,618; a DIR redox compound releasing
coupler, a DIR coupler releasing coupler, a DIR coupler releasing redox
compound, or a DIR redox releasing redox compound described in, e.g.,
JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to
a colored form after being released described in EP 173,302A and 313,308A;
a ligand releasing coupler described in, e.g., U.S. Pat. No. 4,555,477; a
coupler releasing a leuco dye described in JP-A-63-75747; and a coupler
releasing a fluorescent dye described in U.S. Pat. No. 4,774,181.
The couplers for use in this invention can be added to the light-sensitive
material by various known dispersion methods.
Examples of a high-boiling solvent to be used in the oil-in-water
dispersion method are described in e.g. U.S. Pat. No. 2,322,027. Examples
of a high-boiling organic solvent to be used in the oil-in-water
dispersion method and having a boiling point of 175.degree. C. or more at
atmospheric pressure are phthalate esters (e.g., dibutylphthalate,
dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate,
bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate,
bis(1,1-di-ethylpropyl) phthalate); phosphate or phosphonate esters (e.g.,
triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate,
tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate,
tributoxyethylphosphate, trichloropropylphosphate, and
di-2-ethylhexylphenylphosphonate); benzoate esters (e.g.,
2-ethylhexylbenzoate, dodecylbenzoate, and
2-ethylhexyl-p-hydroxybenzoate); amides (e.g., N,N-diethyldodecaneamide,
N,N-diethyllaurylamide, and N-tetradecylpyrrolidone); alcohols or phenols
(e.g., isostearylalcohol and 2,4-di-tertamylphenol), aliphatic carboxylate
esters (e.g., bis(2-ethylhexyl) sebacate, dioctylazelate,
glyceroltriburylate, isostearyllactate, and trioctylcitrate); aniline
derivative (e.g., N,N-dibutyl-2-butoxy-5-tertoctylaniline); and
hydrocarbons (e.g., paraffin, dodecylbenzene, and diisopropylnaph
thalene). An organic solvent having a boiling point of about 30.degree. C.
or more, and preferably, 50.degree. C. to about 160.degree. C. can be used
as an auxiliary solvent. Typical examples of the auxiliary solvent are
ethyl acetate, butyl acetate, ethyl propionate, methylethylketone,
cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
Steps and effects of a latex dispersion method and examples of a loadable
latex are described in, e.g., U.S. Pat. No. 4,199,363 and German Laid-open
Patent Application Nos. 2,541,274 and 2,541,230.
Various types of antiseptics and fungicides are preferably added to the
color light-sensitive material of the present invention. Examples of the
antiseptics and the fungicides are phenetyl alcohol, and
1,2-benzisothiazoline-3-one, n-butyl-p-hydroxybenzoate, phenol,
4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)
benzimidazole described in JP-A-63-257747, JP-A-62-272248, and
JP-A-1-80941.
The present invention can be applied to various color light-sensitive
materials. Examples of the material are a color negative film for a
general purpose or a movie, a color reversal film for a slide or a
television, color paper, a color positive film, and color reversal paper.
A support which can be suitably used in the present invention is described
in, e.g., RD. No. 17643, page 28, RD. No. 18716, from the right column,
page 647 to the left column, page 648, and RD. No. 307105, page 879.
In the light-sensitive material of the present invention, the sum total of
film thicknesses of all hydrophilic colloidal layers at the side having
emulsion layers is preferably 28 .mu.m or less, more preferably, 23 .mu.m
or less, much more preferably, 18 .mu.m or less, and most preferably, 16
.mu.m or less. A film swell speed T1/2 is preferably 30 sec. or less, and
more preferably, 20 sec. or less. The film thickness means a film
thickness measured under moisture conditioning at a temperature of
25.degree. C. and a relative humidity of 55% (two days). The film swell
speed T1/2 can be measured in accordance with a known method in the art.
For example, the film swell speed T1/2 can be measured by using a swell
meter described in Photographic Science & Engineering, A. Green et al.,
Vol. 19, No. 2, pp. 124 to 129. When 90% of a maximum swell film thickness
reached by performing a treatment by using a color developing agent at
30.degree. C. for 3 min. and 15 sec. is defined as a saturated film
thickness, T1/2 is defined as a time required for reaching 1/2 of the
saturated film thickness.
The film swell speed T1/2 can be adjusted by adding a film hardening agent
to gelatin as a binder or changing aging conditions after coating. A swell
ratio is preferably 150% to 400%. The swell ratio is calculated from the
maximum swell film thickness measured under the above conditions in
accordance with a relation: (maximum swell film thickness--film
thickness)/film thickness.
In the light-sensitive material of the present invention, hydrophilic
colloid layers (called back layers) having a total dried film thickness of
2 to 20 .mu.m are preferably formed on the side opposite to the side
having emulsion layers. The back layers preferably contain, e.g., the
light absorbent, the filter dye, the ultraviolet absorbent, the antistatic
agent, the film hardener, the binder, the plasticizer, the lubricant, the
coating aid, and the surfactant described above. The swell ratio of the
back layers is preferably 150% to 500%.
The color photographic light-sensitive material according to the present
invention can be developed by conventional methods described in RD. No.
17643, pp. 28 and 29, RD. No. 18716, the left to right columns, page 651,
and RD. No. 307105, pp. 880 and 881.
A color developer used in development of the light-sensitive material of
the present invention is an aqueous alkaline solution containing as a main
component, preferably, an aromatic primary amine-based color developing
agent. As the color developing agent, although an aminophenol-based
compound is effective, a p-phenylenediamine-based compound is preferably
used. Typical examples of the p-phenylenediamine-based compound are:
3-methyl-4-amino-N,N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniltne,
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethyl aniline, and sulfates,
hydrochlorides and p-toluene sulfonates thereof. Of these compounds,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethyl aniline, is preferred in
particular. These compounds can be used in a combination of two or more
thereof in accordance with the application.
In general, the color developer contains a pH buffering agent such as a
carbonate, a borate, or a phosphate of an alkali metal, and a development
restrainer or an antifoggant such as a chloride, a bromide, an iodide, a
benzimidazole, a benzothiazole, or a mercapto compound. If necessary, the
color developer may also contain a preservative such as hydroxylamine,
diethylhydroxylamine, a sulfite, a hydrazine such as N,N-biscarboxymethyl
hydrazine, a phenylsemicarbazide, triethanolamine, or a catechol sulfonic
acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a
development accelerator such as benzyl alcohol, polyethyleneglycol, a
quaternary ammonium salt or an amine; a dye-forming coupler; a competing
coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a
viscosity-imparting agent; and a chelating agent such as
aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic
acid, or a phosphonocarboxylic acid. Examples of the chelating agent are
ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
nitrilo-N,N,N-trimethylenephosphonic acid,
ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, and
ethylenediamine-di(O-hydroxyphenylacetic acid), and salts thereof.
In order to perform reversal development, black-and-white development is
performed and then color development is performed. As a black-and-white
developer, well-known black-and-white developing agents, e.g., a
dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as
1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol
can be used singly or in a combination of two or more thereof. The pH of
the color and black-and-white developers is generally 9 to 12. Although
the quantity of replenisher of the developer depends on a color
photographic light-sensitive material to be processed, it is generally 3
liters or less per m.sup.2 of the light-sensitive material. The quantity
of replenisher can be decreased to be 500 ml or less by decreasing a
bromide ion concentration in a replenisher. In order to decrease the
quantity of the replenisher, a contact area of a processing tank with air
is preferably decreased to prevent evaporation and oxidation of the
solution upon contact with air.
The contact area of the solution with air in a processing tank can be
represented by an aperture efficiency defined below:
Aperture efficiency= The value of contact area of processing solution with
air represented by cm.sup.2 unit!/ The value of volume of the solution
represented by cm.sup.3 unit!
The above aperture efficiency is preferably 0.1 or less, and more
preferably, 0.001 to 0.05. In order to reduce the aperture efficiency, a
shielding member such as a floating cover may be provided on the surface
of the photographic processing solution in the processing tank. In
addition, a method of using a movable cover described in JP-A-1-82033 or a
slit developing method described in JP-A-63-216050 may be used. The
aperture efficiency is preferably reduced not only in color and
black-and-white development steps but also in all subsequent steps, e.g.,
bleaching, bleach-fixing, fixing, washing, and stabilizing steps. In
addition, the quantity of replenisher can be reduced by using a means of
suppressing storage of bromide ions in the developing solution.
A color development time is normally 2 to 5 minutes. The processing time,
however, can be shortened by setting a high temperature and a high pH and
using the color developing agent at a high concentration.
The photographic emulsion layer is generally subjected to bleaching after
color development. The bleaching may be performed either simultaneously
with fixing (bleach-fixing) or independently thereof. In addition, in
order to increase a processing speed, bleach-fixing may be performed after
bleaching. Also, processing may be performed in a bleach-fixing bath
having two continuous tanks, fixing may be performed before bleach-fixing,
or bleaching may be performed after bleach-fixing, in accordance with the
application. Examples of the bleaching agent are a compound of a
multivalent metal, e.g., iron(III), peroxides; quinones; and a nitro
compound. Typical examples of the bleaching agent are an organic complex
salt of iron(III), e.g., a complex salt of iron(III) and an
aminopolycarboxylic acid such as ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and
glycoletherdiaminetetraacetic acid; or a complex salt of iron(III) and
citric acid, tartaric acid, or malic acid. Of these compounds, an
iron(III) complex salt of aminopolycarboxylic acid such as an iron(III)
complex salt of ethylenediaminetetraacetic acid or
1,3-diaminopropanetetraacetic acid is preferred because it can increase a
processing speed and prevent an environmental contamination. The iron(III)
complex salt of aminopolycarboxylic acid is useful in both the bleaching
and bleach-fixing solutions. The pH of the bleaching or bleach-fixing
solution using the iron(III) complex salt of aminopolycarboxylic acid is
normally 4.0 to 8. In order to increase the processing speed, however,
processing can be performed at a lower pH.
A bleaching accelerator can be used in the bleaching solution, the
bleach-fixing solution, and their pre-bath, if necessary. Useful examples
of the bleaching accelerator are: compounds having a mercapto group or a
disulfide group described in, e.g., U.S. Pat. No. 3,893,858, West German
Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831,
JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631,
JP-A-53-104232, JP-A-53-124424, and JP-A-53-141623, and JP-A-53-28426, and
Research Disclosure No. 17,129 (July, 1978); a thiazolidine derivative
described in JP-A-50-140129; thiourea derivatives described in
JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent 3,706,561;
iodide salts described in West German Patent 1,127,715 and JP-A-58-16235;
polyoxyethylene compounds described in West German Patents 966,410 and
2,748,430; a polyamine compound described in JP-B-45-8836; compounds
described in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727,
JP-A-55-26506, and JP-A-58-163940; and a bromide ion. Of these compounds,
a compound having a mercapto group or a disulfide group is preferable
since the compound has a large accelerating effect. In particular,
compounds described in U.S. Pat. No. 3,893,858, West German Patent
1,290,812, and JP-A-53-95630 are preferred. A compound described in U.S.
Pat. No. 4,552,834 is also preferable. These bleaching accelerators may be
added in the light-sensitive material. These bleaching accelerators are
useful especially in bleach-fixing of a photographic color light-sensitive
material.
The bleaching solution or the bleach-fixing solution preferably contains,
in addition to the above compounds, an organic acid in order to prevent a
bleaching stain. The most preferable organic acid is a compound having an
acid dissociation constant (pKa) of 2 to 5, e.g., acetic acid, propionic
acid, or hydroxy acetic acid.
Examples of the fixing agent to be used in the fixing solution or the
bleach-fixing solution are thiosulfate, a thiocyanate, a thioether-based
compound, a thiourea and a large amount of an iodide. Of these compounds,
a thiosulfate, especially, ammonium thiosulfate can be used in the widest
range of applications. In addition, a combination of thiosulfate and a
thiocyanate, a thioether-based compound, or thiourea is preferably used.
As a preservative of the fixing solution or the bleach-fixing solution, a
sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid
compound described in EP 294,769A is preferred. In addition, in order to
stabilize the fixing solution or the bleach-fixing solution, various types
of aminopolycarboxylic acids or organic phosphonic acids are preferably
added to the solution.
In the present invention, 0.1 to 10 mol/l of a compound having a pKa of 6.0
to 9.0 are preferably added to the fixing solution or the bleach-fixing
solution in order to adjust the pH. Preferable examples of the compound
are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and
2-methylimidazole.
The total time of a desilvering step is preferably as short as possible as
long as no desilvering defect occurs. A preferable time is one to three
minutes, and more preferably, one to two minutes. A processing temperature
is 25.degree. C. to 50.degree. C., and preferably, 35.degree. C. to
45.degree. C. Within the preferable temperature range, a desilvering speed
is increased, and generation of a stain after the processing can be
effectively prevented.
In the desilvering step, stirring is preferably as strong as possible.
Examples of a method of intensifying the stirring are a method of
colliding a jet stream of the processing solution against the emulsion
surface of the light-sensitive material described in JP-A-62-183460, a
method of increasing the stirring effect using rotating means described in
JP-A-62-183461, a method of moving the light-sensitive material while the
emulsion surface is brought into contact with a wiper blade provided in
the solution to cause disturbance on the emulsion surface, thereby
improving the stirring effect, and a method of increasing the circulating
flow amount in the overall processing solution. Such a stirring improving
means is effective in any of the bleaching solution, the bleach-fixing
solution, and the fixing solution. It is assumed that the improvement in
stirring increases the speed of supply of the bleaching agent and the
fixing agent into the emulsion film to lead to an increase in desilvering
speed. The above stirring improving means is more effective when the
bleaching accelerator is used, i.e., significantly increases the
accelerating speed or eliminates fixing interference caused by the
bleaching accelerator.
An automatic developing machine for processing the light-sensitive material
of the present invention preferably has a light-sensitive material
conveyer means described in JP-A-60-191257, JP-A-60-191258, or
JP-A-60-191259.
As described in JP-A-60-191257, this conveyer means can significantly
reduce carry-over of a processing solution from a pre-bath to a post-bath,
thereby effectively preventing degradation in performance of the
processing solution. This effect significantly shortens especially a
processing time in each processing step and reduces the quantity of
replenisher of a processing solution.
The photographic light-sensitive material of the present invention is
normally subjected to washing and/or stabilizing steps after desilvering.
An amount of water used in the washing step can be arbitrarily determined
over a broad range in accordance with the properties (e.g., a property
determined by the materials used, such as a coupler) of the
light-sensitive material, the application of the material, the temperature
of the water, the number of water tanks (the number of stages), a
replenishing scheme representing a counter or forward current, and other
conditions. The relationship between the amount of water and the number of
water tanks in a multi-stage counter-current scheme can be obtained by a
method described in "Journal of the Society of Motion Picture and
Television Engineers", Vol. 64, pp. 248-253 (May, 1955). In the
multi-stage counter-current scheme disclosed in this reference, the amount
of water used for washing can be greatly decreased. Since washing water
stays in the tanks for a long period of time, however, bacteria multiply
and floating substances may be adversely attached to the light-sensitive
material. In order to solve this problem in the process of the color
photographic light-sensitive material of the present invention, a method
of decreasing calcium and magnesium ions can be effectively utilized, as
described in JP-A-62-288838. In addition, a germicide such as an
isothiazolone compound and thiabendazol described in JP-A-57-8542, a
chlorine-based germicide such as chlorinated sodium isocyanurate, and
germicides such as benzotriazole described in Hiroshi Horiguchi et al.,
"Chemistry of Antibacterial and Antifungal Agents", (1986), Sankyo
Shuppan, EiseigiJutsu-Kai ed., "Sterilization, Antibacterial, and
Antifungal Techniques for Microorganisms", (1982), KogyogiJutsu-Kai, and
Nippon Bokin Bokabi Gakkai ed., "Dictionary of Antibacterial and
Antifungal Agents", (1986), can be used.
The pH of the water for washing the photographic light-sensitive material
of the present invention is 4 to 9, and preferably, 5 to 8. The water
temperature and the washing time can vary in accordance with the
properties and applications of the light-sensitive material. Normally, the
washing time is 20 seconds to 10 minutes at a temperature of 15.degree. C.
to 45.degree. C., and preferably, 30 seconds to 5 minutes at 25.degree. C.
to 40.degree. C. The light-sensitive material of the present invention can
be processed directly by a stabilizing agent in place of washing. All
known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345
can be used in such stabilizing processing.
In some cases, stabilizing is performed subsequently to washing. An example
is a stabilizing bath containing a dye stabilizing agent and a
surface-active agent to be used as a final bath of the photographic color
light-sensitive material. Examples of the dye stabilizing agent are
formalin, an aldehyde such as glutaraldehyde, an N-methylol compound,
hexamethylenetetramine, and an adduct of aldehyde sulfite. Various
cheleting agents and fungicides can be added to the stabilizing bath.
An overflow solution produced upon washing and/or replenishment of the
stabilizing solution can be resued in another step such as a desilvering
step.
In the processing using an automatic developing machine or the like, if
each processing solution described above is condensed by evaporation,
water is preferably added to correct condensation.
The silver halide color light-sensitive material of the present invention
may contain a color developing agent in order to simplify processing and
increases a processing speed. For this purpose, various types of
precursors of a color developing agent can be preferably used. Examples of
the precursor are an indoaniline-based compound described in U.S. Pat. No.
3,342,597, Schiff base compounds described in U.S. Pat. No. 3,342,599 and
Research Disclosure (RD) Nos. 14,850 and 15,159, an aldol compound
described in RD No. 13,924, a metal salt complex described in U.S. Pat.
No. 3,719,492, and an urethane-based compound described in JP-A-53-135628.
The silver halide color light-sensitive material of the present invention
may contain various 1-phenyl-3-pyrazolidones in order to accelerate color
development, if necessary. Typical examples of the compound are described
in, for example, JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
Each processing solution in the present invention is used at a temperature
of 10.degree. C. to 50.degree. C. Although a normal processing temperature
is 33.degree. C. to 38.degree. C., processing may be accelerated at a
higher temperature to shorten a processing time, or image quality or
stability of a processing solution may be improved at a lower temperature.
EXAMPLE 1
(Preparation of Emulsions)
First, 30 g of inactive gelatin and 6 g of potassium bromide were dissolved
in 1 liter of distilled water, forming an aqueous solution. While stirring
this aqueous solution and maintaining it at 75.degree. C. , 35 cc of an
aqueous solution containing 5.0 g of silver nitrate, and 35 cc of an
aqueous solution containing 3.2 g of potassium bromide and 0.98 g of
potassium iodide were added at the rate of 70 cc/min over 30 seconds.
Then, pAg was increased to 10, and the solution was repined for 30
minutes, thereby obtaining a seed emulsion.
Further, a predetermined portion of 1 liter of an aqueous solution
containing 145 g of silver nitrate, and an aqueous solution of a mixture
of potassium bromide and potassium iodide were intermittently added, in
equimolar amount each time, at a predetermined temperature and a
predetermined pAg, at a addition speed close to the critical grow speed,
thereby preparing tabular core emulsion. The remainder of the silver
nitrate solution and a solution of a mixture of potassium bromide and
potassium iodide whose compositions are different from those used to
prepare the tabular core solution, were intermittently added, in equimolar
amount each time, at a speed close to the critical growth speed, thus
forming a coating on the cores. As a result, emulsions 1 to 5, each
containing core/shell type grains of silver biomoiodide were prepared.
The aspect ratio of each of emulsions 1 to 5 was adjusted by selecting a
propor aAg value at the time of preparing the core and the shell. The
properties of emulsions 1 to 5, thus prepared, are as is shown in Table 1.
TABLE 1
______________________________________
Average
Average
Average Average Average grain iodine
Emul- aspect aspect grain thickness
content
sion ratio 1) ratio 2) size (.mu.m)
(.mu.m)
(mol %)
______________________________________
1 1.5/1 1.2/1 0.86 0.67 7.6
2 2.8/1 2.2/1 1.01 0.55 7.6
3 4.6/1 3.6/1 1.63 0.36 7.6
4 6.7/1 5.2/1 1.74 0.30 7.6
5 11.7/1 9.8/1 2.10 0.21 7.6
______________________________________
1) An average value of the aspect ratios of individual grains obtained as
follows; the projected area of 1000 grains are measured and the measure
value are summed in the order of the measured value from the greatest one
to the lowest one, until the summed projected area reach 50% of the
projected areas of all grains.
2) An average value of the aspect ratios of the grains corresponding to
85% of the projected areas of all grains which is obtained by the same
method as above.
A plurality of layers having the following compositions were coated on an
undercoated triacetylcellulose film support, forming a multilayered color
light-sensitive material (hereinafter referred to as "Sample 101").
(Compositions of light-sensitive layers)
Numerals corresponding to each component indicates a coating amount
represented in units of g/m.sup.2. The coating amount of a silver halide
is represented by the coating amount of silver. The coating amount of a
sensitizing dye is represented in units of moles per mole of a silver
halide in the same layer.
(Sample 101)
______________________________________
Layer 1: Antihalation layer
Black colloidal silver
silver 0.18
Gelatin 0.50
Layer 2: Inter-layer
2,5-di-t-pentadecylhydroquinone
0.18
EX-1 0.18
EX-3 0.020
EX-12 2.0 .times. 10.sup.-3
U-1 0.060
U-2 0.080
U-3 0.10
HBS-1 0.10
HBS-2 0.020
Gelatin 0.80
Layer 3: First red-sensitive emulsion layer
Emulsion A silver 0.15
Emulsion B silver 0.35
Sensitizing dye I 6.9 .times. 10.sup.-5
Sensitizing dye II 1.8 .times. 10.sup.-5
Sensitizing dye III 3.1 .times. 10.sup.-4
EX-2 0.17
EX-10 0.020
EX-14 0.17
U-1 0.070
U-2 0.050
U-3 0.070
HBS-1 0.020
Gelatin 0.75
Layer 4: Second red-sensitive emulsion layer
Emulsion G silver 0.30
Emulsion D 0.50
Sensitizing dye I 5.1 .times. 10.sup.-5
Sensitizing dye II 1.4 .times. 10.sup.-5
Sensitizing dye III 2.3 .times. 10.sup.-4
EX-2 0.20
EX-3 0.050
EX-10 0.015
EX-14 0.20
EX-15 0.050
U-1 0.020
U-2 0.010
U-3 0.020
Gelatin 1.00
Layer 5: Third red-sensitive emulsion layer
Emulsion 1 silver 1.40
Sensitizing dye I 5.4 .times. 10.sup.-5
Sensitizing dye II 1.4 .times. 10.sup.-5
Sensitizing dye III 2.4 .times. 10.sup.-4
Exemplified compound (11) 6.0 .times. 10.sup.-4
EX-16 0.070
EX-2 0.097
EX-3 0.010
EX-4 0.080
HBS-1 0.10
HBS-2 0.10
Gelatin 1.30
Layer 6: Inter-layer
EX-17 0.060
HBS-1 0.020
Gelatin 0.50
Layer 7: First green-sensitive emulsion layer
Emulsion A silver 0.10
Emulsion B silver 0.20
Sensitizing dye IV 3.0 .times. 10.sup.-5
Sensitizing dye V 1.0 .times. 10.sup.-4
Sensitizing dye VI 3.8 .times. 10.sup.-4
EX-1 0.021
EX-6 0.26
EX-7 0.030
EX-8 0.010
Compound (CB-3) of invention 0.030
HBS-1 0.10
HBS-3 0.010
Gelatin 0.63
Layer 8: Second green-sensitive emulsion layer
Emulsion C silver 0.25
Emulsion E silver 0.20
Sensitizing dye IV 2.1 .times. 10.sup.-5
Sensitizing dye V 7.0 .times. 10.sup.-5
Sensitizing dye VI 2.6 .times. 10.sup.-4
EX-6 0.094
EX-7 0.026
EX-8 0.015
Compound (CB-3) of invention 0.025
HBS-1 0.16
HBS-3 8.0 .times. 10.sup.-3
Gelatin 0.50
Layer 9: Third green-sensitive emulsion layer
Emulsion 1 silver 1.20
Sensitizing dye IV 3.5 .times. 10.sup.-5
Sensitizing dye V 8.0 .times. 10.sup.-5
Sensitizing dye VI 3.0 .times. 10.sup.-4
EX-1 0.013
EX-11 0.065
EX-13 0.019
Compound (CB-3) of invention 0.010
HBS-1 0.05
HBS-2 0.10
Gelatin 1.00
Layer 10: Yellow filter layer
Yellow colloid silver 0.050
EX-5 0.080
HBS-1 0.030
Gelatin 0.50
Layer 11: First blue-sensitive emulsion layer
Emulsion A silver 0.080
Emulsion B silver 0.070
Emulsion F silver 0.070
Sensitizing dye VII 3.5 .times. 10.sup.-4
EX-8 0.085
EX-9 0.72
HBS-1 0.20
Gelatin 1.10
Layer 12: Second blue-sensitive emulsion layer
Emulsion 1 silver 0.45
Sensitizing dye VII 2.1 .times. 10.sup.-4
EX-8 0.050
EX-9 0.15
EX-10 7.0 .times. 10.sup.-3
HBS-1 0.050
Gelatin 0.50
Layer 13: Third blue-sensitive emulsion layer
Emulsion H silver 0.50
Emulsion G silver 0.20
Sensitizing dye VII 2.2 .times. 10.sup.-4
Exemplified compound (18) 5.0 .times. 10.sup.-4
EX-9 0.20
HBS-1 0.070
Gelatin 0.69
Layer 14: First protective layer
Emulsion I silver 0.20
U-4 0.11
U-5 0.17
HBS-1 5.0 .times. 10.sup.-2
Gelatin 1.00
Layer 15: Second protective layer
H-1 0.40
B-1 (diameter: 1.7 .mu.m) 5.0 .times. 10.sup.-2
B-2 (diameter: 1.7 .mu.m) 0.10
B-3 0.10
S-1 0.20
Gelatin 0.60
______________________________________
Further, all layers of Sample 101 contained W-1, w-2, W-3, B-4, B-5, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, iron salt,
lead salt, gold salt, platinum salt, iridium salt, and rhodium salt, so
that they may have improved storage stability, may be more readily
processed, may be more resistant to pressure, more antibacterial and more
antifungal, may be better protected against electrical charging, and may
be more readily coated.
The structures of the compounds used in Sample 101 are as follows:
##STR23##
The emulsions A to I used in Sample 101 are as is shown in the following
Table 2:
TABLE 2
__________________________________________________________________________
Average
Average
Variation Coeffi-
Diameter/
AgI Con-
Grain cient Relating to
Thickness
Silver Amount Ratio
tent (%)
Size (.mu.m)
Grain Size (%)
Ratio (AgI Content %)
__________________________________________________________________________
Emulsion A
4.0 0.45 27 1 Core/Shell = 1/3 (13/1),
Double structure grain
Emulsion B
8.9 0.70 14 1 Core/Shell = 3/7 (25/2),
Double structure grain
Emulsion C
10 0.75 17 1 Core/Shell = 1/2 (24/3),
Double structure grain
Emulsion D
16 0.95 22 1 Core/Shell = 4/6 (40/0),
Double structure grain
Emulsion E
10 0.95 18 1 Core/Shell = 1/2 (24/3),
Double structure grain
Emulsion F
4.0 0.25 28 1 Core/Shell = 1/3 (13/1),
Double structure grain
Emulsion G
14.0 0.75 17 1 Core/Shell = 1/2 (42/0),
Double structure grain
Emulsion H
14.5 1.20 18 1 Core/Shell = 37/63 (34/3),
Double structure grain
Emulsion I
1 0.07 15 1 Uniform grain
__________________________________________________________________________
(Samples 102 to 105)
Samples 102 to 105 were prepared which were identical to Sample 101, except
that their layers 5 and 9 were not formed of emulsion 1, but of emulsions
2 to 5, respectively.
(Samples 106 to 110)
Samples 106 to 110 were prepared which were identical to Samples 101 to
105, except that the layers 8 and 9 contained the compound (C-1) specified
below, respectively, in place of the compound (CB-3) of the invention.
##STR24##
(Samples 111 to 118)
Samples 111 to 118 were prepared which were identical to Sample 108, except
that the layers 8 and 9 contained the compounds shown in Table 4,
respectively, in place of the compound (C-1) of the invention. These
compounds were added in such amounts that the layers 8 and 9 had
substantially the same gamma value.
(Sample 119)
Sample 119 was prepared which was identical to Sample 118, except that
neither the compound (11) nor the compound (18) were not used at all.
Samples 101 to 119, thus prepared, were exposed imagewise to white light.
Then, they were color-developed in the conditions which will be specified
later. The relative sensitivity of each sample were evaluated, as the
logarithmic value of the reciprocal of the exposure amount which achieved
magenta density of fog +0.5. Also, the samples were left to stand at
45.degree. C. and relative humidity of 80% for 7 days, and developed,
thereby detecting the change in fog occurring during the 7-day period.
Further, the RMS value of each sample, indicating the graininess, (i.e., a
value at the magenta density (fog +0.5) at aperture of 48 .mu.m diameter)
was measured. Also, the MTF value of the magenta image formed on each
sample, which represents the sharpness, was measured. Still further, the
samples were uniformly exposed to blue light at 1 lux/sec and then exposed
imagewise to green light. The color turbidities were shown in Table 3,
which was obtained by subtracting the yellow densities in the magenta fog
densities from the yellow densities in the exposure amounts which provide
magenta densities equal to the value of (fog +1.0).
TABLE 3
__________________________________________________________________________
Emulsion
Emulsion RMS MTF value
of layers
of layers
Compound
Compound
Relative
value
(magent image)
Color
Change
Sample 5, 9 and 12
7, 8 and 9
in layer 5
in layer 13
sensitivity
.times.1000
25 cycles/mm
turbidity
in
__________________________________________________________________________
Fog
101 (Comp.)
1 CB-3 (11) (18) 0.00 28.5
0.61 -0.07
0.04
102 (Invention)
2 " " " 0.00 27.4
0.63 -0.05
0.02
103 (Invention)
3 " " " 0.01 26.9
0.65 -0.04
0.02
104 (Invention)
4 " " " 0.02 26.9
0.65 -0.04
0.02
105 (Invention)
5 " " " 0.03 26.8
0.65 -0.04
0.02
106 (Comp.)
1 C-1 " " -0.03 29.1
0.57 -0.02
0.08
107 (Comp.)
2 " " " -0.03 28.1
0.59 -0.01
0.07
108 (Comp.)
3 " " " -0.02 27.5
0.61 0.00 0.07
109 (Comp.)
4 " " " -0.01 27.5
0.61 0.00 0.07
110 (Comp.)
5 " " " 0.00 27.5
0.61 0.00 0.07
111 (Comp.)
3 C-2 (11) (18) -0.01 27.3
0.61 0.00 0.08
112 (Comp.)
3 C-3 " " 0.00 27.6
0.60 0.01 0.10
113 (Comp.)
3 C-4 " " 0.00 27.6
0.60 0.03 0.08
114 (Invention)
3 CA-1 " " 0.02 26.8
0.63 -0.02
0.04
115 (Invention)
3 CA-19 " " 0.02 26.8
0.63 -0.02
0.03
116 (Invention)
3 CB-2 " " 0.02 26.9
0.65 -0.04
0.02
117 (Invention)
3 CB-16 " " 0.02 26.9
0.64 -0.04
0.02
118 (Invention)
3 CB-18 " " 0.02 26.8
0.65 -0.04
0.02
119 (Invention)
3 " -- -- 0.00 27.2
0.65 -0.04
0.04
__________________________________________________________________________
Samples 101 to 119 were color-developed by means of an automatic developing
machine, by the method specified below, until the accumulated quantity of
replenisher reached three times the volume of the mother solution tank.
______________________________________
Processing Method
Quantity* of
Tank
Process Time Temp. replenisher
volume
______________________________________
Color 3 min. 15 sec.
38.degree. C.
33 ml. 20 l
development
Bleaching 6 min. 30 sec.
38.degree. C.
25 ml 40 l
Washing 2 min. 10 sec.
24.degree. C.
1200 ml 20 l
Fixing 4 min. 20 sec.
38.degree. C.
25 ml 30 l
Washing (1)
1 min. 05 sec.
24.degree. C.
** 10 l
Washing (2)
1 min. 00 sec.
24.degree. C.
1200 ml 10 l
Stabilization
1 min. 05 sec.
38.degree. C.
25 ml 10 l
Drying 4 min. 20 sec.
55.degree. C.
______________________________________
*Note:
The quantity of replenisher is per meter of a 35mm wide sample.
**Note:
The washing (1) was carried out in counter flow, from the step (2) to the
step (1).
The compositions of the solutions used in the color-developing process are
as follows:
______________________________________
Mother So-
Replenisher
lution (g)
(g)
______________________________________
(Color Developing Solution):
Diethylenetriamine-
1.0 1.1
pentaacetate
1-hydroxyethylidene-
3.0 3.2
1,1-diphosphonic acid
Sodium sulfite 4.0 4.4
Potassium carbonate
30.0 37.0
Potassium bromide 1.4 0.7
Potassium iodide 1.5 mg --
Hydroxylamine sulfate
2.4 2.8
4- N-ethyl-N-.beta.-
4.5 5.5
hydroxylethylamino!
2-methylaniline
sulfate
Water to make 1.0 l 1.0 l
pH 10.05 10.10
(Bleaching Solution):
Sodium ferric 100.0 120.0
ethylenediamine
tetraacetate trihydrate
Disodium ethylene-
10.0 10.0
diamine tetraacetate
Ammonium bromide 140.0 160.0
Ammonium nitrate 30.0 35.0
Ammonia water (27%)
6.5 ml 4.0 ml
Water to make 1.0 l 1.0 l
pH 6.0 5.7
(Fixing Solution):
Disodium ethylene-
0.5 0.7
diamine tetraacetate
Sodium sulfite 7.0 8.0
Sodium bisulfite 5.0 5.5
Ammonium thiosulfate
170.0 ml 200.0 ml
aqueous solution (70%)
Water to make 1.0 l 1.0 l
pH 6.7 6.6
(Stabilizing Solution):
Formalin (37%) 2.0 ml. 3.0 ml
Polyoxyethylene-p-
0.3 0.45
monononylphenyl-
ether (polymeri-
zation degree: 10)
Disodium ethylenedi-
0.05 0.08
amine tetraacetate
Water to make 1.0 l 1.0 l
pH 5.0-8.0 5.0-8.0
______________________________________
As is evident from Table 3, the samples according to the present invention
had high sensitivity, excelled in graininess, sharpness and color
reproduction, and had their fog changed little while being stored. In
particular, the samples which contained the compounds (11) and (18)
exhibited good graininess, sensitivity, and storage stability.
EXAMPLE 2
Emulsion 6 (This Invention)
First, 25 cc of gelatin-containing 2M silver nitrate aqueous solution and
25 cc of gelatin-containing 2M potassium bromide aqueous solution were
simultaneously added to 1 liter of 0.7 wt % gelatin solution containing
0.04M of potassium bromide over 1 minutes, while vigorously stirring the
gelatin solution at 30.degree. C. The resultant mixture solution was
heated to 75.degree. C., and 300 cc of 10-wt % gelatin solution was added
to the solution. Thereafter, 30 cc of 1M silver nitrate aqueous solution
was added over 5 minutes and then 10 cc of 25-wt % ammonia water was added
to the solution. The resultant mixture solution was ripened at 75.degree.
C. After the ripening, ammonia was neutralized and, 1M silver nitrate
aqueous solution and 1M potassium bromide aqueous solution were added to
and mixed with the solution at an increasing rate (The final rate was 5
times the initial rate), while maintaining the solution at 2.3 pBr. The
amount of the silver nitrate aqueous solution used was 600 cc. The
emulsion, thus prepared, was washed with ordinary flocculation, and
dispersed gelatin was added to the emulsion, thereby preparing 800 g of
silver halide emulsion (i.e., seed emulsion A) containing hexagonal
tabular grains. The seed emulsion A contained monodispersed hexagonal
tabular grains which had average equivalent-circle diameter (grain size)
of 1.0 .mu.m, average thickness of 0.18 .mu.m, and variation coefficient
of 11%. Next, 800 cc of distilled water, 30 g of gelatin, and 6.5 g of
potassium bromide were added to 250 g of seed emulsion A, thus forming a
solution. This solution was heated to 75.degree. C. and subsequently
stirred. 1M silver nitrate aqueous solution and 1M silver halide alkali
aqueous solution (containing 90 mol % of potassium bromide and 10 mol % of
potassium iodide) were simultaneously added to the solution, at an
increasing rate (The final rate was 3 times the initial rate), while
maintaining the solution at 1.6 pBr, thereby mixing the silver nitrate
aqueous solution and the silver halide alkali aqueous solution with the
solution. The amount of the silver nitrate aqueous solution used was 600
cc. Further, 1M silver nitrate aqueous solution and 1M potassium bromide
aqueous solution were simultaneously added to the resultant solution at an
increasing rate (The final rate was 1.5 times the initial rate), while
maintaining the solution at pBr 1.6. The amount of the silver nitrate
aqueous solution used was 200 cc.
The emulsion thus obtained was washed with water by the above-mentioned
method. Dispersed gelatin was added to the emulsion, thereby preparing
silver halide emulsion containing monodispersed hexagonal tabular grains
(emulsion 6). The hexagonal tabular grains occupied 92% of the total
projected area of all grains contained in emulsion 6, had an average grain
size of 1.75 .mu.m, an average thickness of 0.29 .mu.m, an average aspect
ratio of 6:1, and a variation coefficient of 16%.
Emulsion 7 (This Invention)
Seed emulsion B was obtained by the same method as in the preparation of
emulsion 6, except that 1M silver nitrate aqueous solution for the second
time and ammonia water were added in an amount of 20 cc and an amount of 8
cc, respectively. The grains in the seed emulsion B were grown in the same
way as in the preparation of emulsion 6, except that pBr was maintained at
1.5 during the growth of grains. As a result, emulsion 7 was prepared
which contained hexagonal tabular grains occupying 90% of the total
projected area of all grains. The hexagonal tabular grains had an average
size of 2.1 .mu.m, an average thickness of 0.21 .mu.m, an average aspect
ratio of 10:1 and a variation coefficient of 19%.
Emulsion 8 (This Invention)
Seed emulsion C was obtained by the same method as in the preparation of
emulsion 6, except that 1M silver nitrate aqueous solution for the second
time was added in an amount of 10 cc, not 30 cc, and no ammonia water was
added at all, and that pBr for the third time was maintained at 1.7, not
2.3. Then, the grains in the seed emulsion C were grown in the same way as
in the preparation of emulsion 6. As a result, emulsion 8 was prepared
which contained hexagonal tabular grains occupying 62% of the total
projected area of all grains. The hexagonal tabular grains had an average
size of 2.0 .mu.m, an average thickness of 0.17 .mu.m, an average aspect
ratio of 12:1, and a variation coefficient of 37%.
A mixture of the sensitizing dyes IV, V, and VI used in ratio of
0.2:0.1:0.3 was added to emulsions 6, 7, 8, and 1 in such an amount which
was 70% of the saturated adsorption amount to each emulsion. Emulsions 6,
7, 8 and 1 were left to stand for 20 minutes at 60.degree. C., and were
then appropriately sensitized chemically with sodium thiosulfate,
chloroauric acid, and potassium thiocyanate at 60.degree. C. at pH value
of 6.5. As a result, emulsions 6-1, 7-1, 8-1, and 1-1 were prepared, the
properties of which were as is shown in the following Table 4.
TABLE 4
__________________________________________________________________________
Variation
Ratio of
Relative standard
Average
Average
Average
Average
Average
Coefficient
hexagonal
deviation of
aspect
aspect
aspect
grain
grain
Relating to
tabular
intra-grain of
Emulsion
ratio 1)
ratio 2)
ratio 3)
size (.mu.m)
size (.mu.m)
grain size
grains (%)
AgI content
__________________________________________________________________________
6-1 7.9/1
7.2/1
6.0/1
1.75 0.29 0.15 92 13
7-1 13/1
11/1
10/1
2.10 0.21 0.19 90 16
8-1 21/1
17/1
12/1
2.00 0.17 0.37 62 24
1-1 1.5/1
1.2/1
1.1/1
0.86 0.67 0.25 10 22
__________________________________________________________________________
1), 2) These are values measured in the same way as those shown in Table
1.
3) The average value for all grains contained in the emulsion.
4) Ratio of the total projected area of hexagonal grains to that of all
grains.
5) The values measured by the method disclosed in JPA-60-143332.
(Samples 201 to 204)
Samples 201 to 204 were prepared in the same method as Sample 101, except
that emulsions 6-1, 7-1, 8-1, and 1-1 were used in the layer 9, in place
of emulsion 1, that the sensitizing dyes IV, V, VI were not used in the
layer 9 at all, and that the compound (CB-3) of this invention was added
to the layer 5 in an amount of 0.015 g/m.sup.2.
(Samples 205 to 208)
Samples 205 to 208 were prepared in the same way as Samples 201 to 204,
respectively, except that the compound (CB-18) was added to the layers 5,
7, 8 and 9, in place of the compound (CB-3) in an equimolar amount.
(Samples 209 and 210)
Samples 209 and 210 were prepared in the same way as Sample 205, except
that emulsion 6-1 and another emulsion was added in an mixing ratio of
1:1.
Samples 201 to 210, thus prepared, were processed in the method specified
below, for their relative sensitivities, their MTF values of magenta
images, and their RMS values. The results were as is shown in the
following Table 5.
______________________________________
Processing Method
Quantity* of
Tank
Process Time Temp. replesnisher
volume
______________________________________
Color 3 min. 15 sec.
37.8.degree. C.
25 ml 10 l
development
Bleaching 45 sec. 38.degree. C.
5 ml 4 l
Bleach- 45 sec. 38.degree. C.
-- 4 l
fixing (1)
Bleach- 45 sec. 38.degree. C.
30 ml 4 l
fixing (2)
Washing (1)
20 sec. 38.degree. C.
-- 2 l
Washing (2)
20 sec. 38.degree. C.
30 ml 2 l
Stabili- 20 sec. 38.degree. C.
20 ml 2 l
zation
Drying 1 min. 55.degree. C.
______________________________________
*Note:
The quantity of replenisher is per meter of a 35mm wide sample.
The bleach fixing and washing step were carried out in counter flow, from
the step (2) to the step (1), and the overflowing bleach solution was used
in the bleach fixing (2).
The amount of the bleach-fixing solution left over to the washing was 2 ml
per meter of the 35 mm wide light-sensitive material.
______________________________________
Mother So-
Replenisher
lution (g)
(g)
______________________________________
(Color Developing Solution):
Diethylenetriamine-
5.0 6.0
pentaacetate
Sodium sulfite 4.0 5.0
Potassium carbonate
30.0 37.0
Potassium bromide 1.3 0.5
Potassium iodide 1.2 mg --
Hydroxylamine sulfate
2.0 3.6
4- N-ethyl-N-.beta.-
4.7 6.2
hydroxyethylamino!
2-methylaniline
sulfate
Water to make 1.0 l 1.0 l
pH 10.00 10.15
(Bleaching Solution):
Ammonium ferric 1,3-
144.0 206.0
diaminopropane
tetraacetate
monohydrate
1,3-diaminopropane
2.8 4.0
tetraacetic acid
Ammonium bromide 84.0 120.0
Ammonium nitrate 17.5 25.0
Ammonia water (27%)
10.0 ml 1.8 ml
Acetic acid (98%) 51.1 73.0
Water to make 1.0 l 1.0 l
pH 4.3 3.4
(Bleach-fixing Solution):
Ammonium ferric 50.0 --
ethylenediamine
tetraacetate
dihydrate
Disodium ethylene-
5.0 25.0
diamine tetraacetate
Ammonium sulfite 12.0 20.0
Ammonium thiosulfate
290.0 ml 320.0 ml
aqueous solution
(700 g/l)
Ammonia water (27%)
6.0 ml 15.0 ml
Water to make 1.0 l 1.0 l
______________________________________
(Washing Solution): The same solution used for mother solution and the
replenisher
(Washing Solution): The same solution used for mother solution and the
replenisher
The washing solution was prepared by passing tap water through a mixed-bed
column filled with H-type strong-acid cation exchange resin (Amberlite
IR-120B of Rohm and Haas, Inc.) and OH-type strong-base anion exchange
resin (Amberlite IRA-400 of Rohm and Haas, Inc.), thereby adjusting the
calcium and magnesium ion concentrations to 3 mg/l or less, and then by
adding 20 mg/l of dichloro isocyanurate and 150 mg/l of sodium sulfate
were added to the water thus processed, thereby obtaining the washing
solution. The washing solution had pH value ranging from 6.5 to 7.5.
______________________________________
(Stabilizing Solution): The same solution
used for mother solution and replenisher (unit g)
Surfactant 1.2 ml
C.sub.10 H.sub.21--O(CH.sub.2 CH.sub.2 O.sub.10--H!
Ethyleneglycol 0.4
Water to make 1.0 l
pH 5.0 to 7.0
______________________________________
TABLE 5
______________________________________
Emulsion Emulsion RMS
of in layers 5,
Relative
value MTF
Sample layer 9 7, 8 and 9
sensitivity
.times.1000
value
______________________________________
201 6-1 CB-3 0.00 26.8 0.63
(Invention)
202 7-1 " 0.03 27.0 0.64
(Invention)
203 8-1 " -0.02 27.2 0.64
(Invention)
204 1-1 " -0.05 28.9 0.61
(Comp.)
205 6-1 CB-18 0.01 26.9 0.64
(Invention)
206 7-1 " 0.03 27.1 0.65
(Invention)
207 8-1 " -0.02 27.2 0.65
(Invention)
208 1-1 " -0.05 29.0 0.61
(Comp.)
209 6-1/7-1 " 0.02 27.0 0.65
(Invention)
210 6-1/9-1 " -0.01 27.6 0.63
(Invention)
______________________________________
As is evident from Table 5, the samples of the invention had higher
sensitivities and better graininesses than the samples using the emulsions
which fell outside the scope of the present invention. In particular, the
samples using emulsions 6-1 and 7-1 which contained many hexagonal tabular
grains excelled in sensitivity and graininess.
EXAMPLE 3
Preparation of Emulsions
An aqueous solution was prepared by dissolving 6 g of potassium bromide and
23 g of inactive gelatin in 3.7 liters of distilled water. While this
solution was stirred, 14% potassium bromide aqueous solution and 20%
silver nitrate aqueous solution were added to the solution at a prescribed
flow rate over 1 minute at 45.degree. C. and pAg value of 9.6 by means of
double-jet method, thus forming a mixture solution. (In this addition (I),
2.40% of all silver used was consumed.) Next, 3300 cc of 17% gelatin
aqueous solution was added to the mixture solution. The solution was
stirred at 45.degree. C. Then, 20% silver nitrate aqueous solution was
added at a predetermined flow rate, until the pAg value reached 8.40. (In
this addition (II), 5.0% of all silver used was consumed.) The resultant
solution was heated to 75.degree. C., and 35 .mu.l of 25% NH.sub.3 aqueous
solution was added to the solution. The solution was left to stand for 15
minutes. Thereafter, 510 .mu.l of 1N H.sub.2 SO.sub.4 was added, thereby
neutralizing the solution. Further, 20% potassium bromide solution
containing potassium iodide and 33% silver nitrate aqueous solution were
added to the solution over 80 minutes by means of double-jet method, thus
adding 8.3 g of potassium iodide, thereby forming an emulsion. (In this
addition (III), 92.6% of all silver used was consumed.) During the
addition (III), the solution was maintained at 75.degree. C. and pAg value
of 8.10. The total amount of silver nitrate used in the emulsion was 425
g. The emulsion was desilvered by ordinary flocculation, and was subjected
to an appropriate gold-sulfur sensitization in the presence of sensitizing
dyes S'-5 and S'-6, thereby preparing tabular AgBrI emulsion 1' (AgI=2.0
mol %).
Emulsion 2' was prepared in the same way as emulsion 1', except that in the
addition (III), potassium bromide aqueous solution containing no potassium
iodide and silver nitrate aqueous solution were added to the solution
until 40% of all silver used was consumed. Then, the addition of silver
nitrate and potassium bromide solutions was stopped and 830 ml of 1%
potassium iodide aqueous solution was added to the solution over about 90
seconds. Thereafter, the remainder of the potassium bromide and silver
nitrate aqueous solutions was added to the solution at 3 times the flow
rate.
Emulsion 3' was prepared by the same method as emulsion 2', except that
potassium bromide aqueous solution was added to the solution just before
adding potassium iodide aqueous solution, and that the pAg value was
adjusted to 9.0.
Emulsion 4' was prepared in the same way as emulsion 2', except that the
temperature of the solution was set at 30.degree. C. just before potassium
iodide aqueous solution was added to the solution. Potassium bromide and
silver nitrate aqueous solutions were added after the addition of the
potassium iodide aqueous solution, by double-jet method at 30.degree. C.
and pAg value of 8.1.
Emulsions 1' to 4', thus prepared, contained grains having
equivalent-sphere diameters of about 0.7 .mu.m and a ratio of average
grain diameter/grain thickness of 6.5 to 7.0.
Emulsions 1' to 4' were directly examined by the method used in in Example
1-(2) described in JP-A-63-220238,by means of a transmission electron
microscope, to see whether or not dislocation had occurred in the grains.
No dislocation was found in the grains contained in emulsion 1'. Ten or
more dislocation lines were observed in 50% or more of the grains
contained in emulsions 2' to 4'. Unlike in the grains of emulsion 2', a
similar number of dislocation lines were observed in the grains of
emulsions 3' and 4'.
Intra-grain iodine distribution of emulsions 1' and 4' were further
evaluated by the methods described in European Patent 147868A. The results
were as is shown in the following Table 6:
TABLE 6
______________________________________
Emulsion 1' 2' 3' 4'
______________________________________
Intra-grain 20 65 30 15
Distribution of
iodine (%)
______________________________________
Preparation of Sample 301
A plurality of layers having the following compositions were coated on a
triacetylcellulose film support undercoated on both sides and having a
thickness of 205 .mu.m, thereby forming a multilayered color
light-sensitive material (hereinafter referred to as "Sample 301").
(Compositions of light-sensitive layers)
Numerals corresponding to each component indicates a coating amount
represented by the values per 1 m.sup.2 of the sample. The coating amount
of a silver halide and colloidal silver are represented by the coating
amount of silver.
(Sample 301)
______________________________________
Layer 1: Antihalation layer
Black colloidal silver 0.25 g
Gelatin 1.9 g
UV absorbent U'-1 0.04 g
UV absorbent U'-2 0.1 g
UV absorbent U'-3 0.1 g
UV absorbent U'-4 0.1 g
UV absorbent U'-6 0.1 g
Additive P-1 0.1 g
Additive F'-10 0.2 g
Organic solvent having a 0.1 g
high-boiling point Oil-1
Layer 2: Inter-layer
Gelatin 0.40 g
Compound Cpd-D 10 mg
Dye D-4 0.4 mg
Organic solvent having 40 mg
a high-boiling point Oil-3
Dye D-6 0.1 g
Layer 3: Inter-layer
Additive M-1 0.05 g
Gelatin 0.4 g
Layer 4: Low red-sensitive emulsion layer
Emulsion A' silver 0.2
g
Emulsion B' silver 0.3
g
Additive F'-14 1 mg
Gelatin 0.8 g
Compound Cpd-K 0.05 g
Coupler C'-1 0.15 g
Coupler C'-2 0.05 g
Coupler C'-9 0.05 g
Coupler C'-10 0.10 g
Compound Cpd-D 10 mg
Additive F'-2 0.1 mg
Organic solvent having 0.10 g
a high-boiling point Oil-2
Additive F'-12 0.5 mg
Layer 5: Medium red-sensitive emulsion layer
Emulsion B' silver 0.2
g
Emulsion C' silver 0.3
g
Gelatin 0.8 g
Additive F'-13 0.05 mg
Coupler C'-1 0.2 g
Coupler C'-2 0.05 g
Coupler C'-3 0.2 g
Additive F'-2 0.1 mg
Organic solvent having 0.1 g
a high-boiling point Oil-2
Layer 6: High red-sensitive emulsion layer
Emulsion D' silver 0.4
g
Gelatin 1.1 g
Coupler C'-3 0.7 g
Coupler C'-1 0.3 g
Additive P-1 0.1 g
Additive F'-1 0.1 mg
Layer 7: Inter-layer
Gelatin 0.6 g
Color-mixing inhibitor Cpd-L
0.05 g
Additive F'-1 1.5 mg
Additive F'-7 2.0 mg
Additive Cpd-N 0.02 g
Additive M-1 0.3 g
Color-mixing inhibitor Cpd-K
0.05 g
UV absorbent U'-1 0.1 g
UV absorbent U'-6 0.1 g
Dye D'-1 0.02 g
Dye D'-6 0.05 g
Layer 8: Inter-layer
Silver bromoiodide emulsion con-
silver 0.02
g
taining surface- and internally-fogged
grains (av. grain size: 0.06 .mu.m;
variation coefficient: 16%;
AgI content: 0.3 mol %)
Gelatin 1.0 g
Additive P-1 0.2 g
Color-mixing inhibitor Cpd-J
0.1 g
Color-mixing inhibitor Cpd-M
0.05 g
Color-mixing inhibitor Cpd-A
0.1 g
Layer 9: Low green-sensitive emulsion layer
Silver bromoiodide emulsion
silver 0.05
g
containing internally-fogged
grains (av. grain size: 0.1 .mu.m;
AgI content: 0.1 mol %)
Emulsion E' silver 0.3
g
Emulsion F' silver 0.1
g
Emulsion G' silver 0.1
g
Gelatin 0.5 g
Coupler C'-4 0.20 g
Coupler C'-7 0.10 g
Coupler C'-8 0.10 g
Coupler C'-11 0.10 g
Compound Cpd-B 0.03 g
Compound Cpd-E 0.02 g
Compound Cpd-F 0.02 g
Compound Cpd-G 0.02 g
Compound Cpd-H 0.02 g
Compound Cpd-D 10 mg
Additive F'-5 0.1 mg
Additive F'-3 0.2 mg
Additive F'-11 0.5 mg
Organic solvent having 0.2 g
a high-boiling Oil-2
Layer 10: Medium green-sensitive emulsion layer
Emulsion G' silver 0.3
g
Emulsion H' silver 0.1
g
Gelatin 0.6 g
Coupler C'-4 0.1 g
Coupler C'-7 0.1 g
Coupler C'-8 0.1 g
Coupler C'-11 0.05 g
Compound Cpd-B 0.03 g
Compound Cpd-E 0.02 g
Compound Cpd-F 0.02 g
Compound Cpd-G 0.05 g
Compound Cpd-H 0.05 g
Additive F'-5 0.08 mg
Organic solvent having 0.01 g
a high-boiling point Oil-2
Layer 11: High green-sensitive emulsion layer
Emulsion I' silver 0.5
g
Gelatin 1.1 g
Coupler C'-4 0.4 g
Coupler C'-7 0.2 g
Coupler C'-8 0.2 g
Coupler C'-12 0.1 g
Coupler C'-9 0.05 g
Compound Cpd-B 0.08 g
Compound Cpd-E 0.02 g
Compound Cpd-F 0.02 g
Compound Cpd-G 0.02 g
Compound Cpd-H 0.02 g
Additive F'-2 0.3 mg
Organic solvent having 0.04 g
a high-boiling point Oil-2
Additive F'-13 0.05 mg
Layer 12: Inter-layer
Gelatin 0.8 g
Additive F'-1 2.0 mg
Additive F'-8 2.0 mg
Dye D'-1 0.1 g
Dye D'-3 0.07 g
Dye D'-8 0.03 g
Dye D'-2 0.05 g
Layer 13: Yellow filter layer
Yellow colloidal silver silver 0.1
g
Gelatin 1.3 g
Dye D'-5 0.05 g
Color-mixing inhibitor Cpd-A
0.01 g
Additive F'-4 0.3 mg
Organic solvent having 0.01 g
a high-boiling point Oil-1
Dye D'-7 0.03 g
Additive M-2 0.01 g
Layer 14: Inter-layer
Gelatin 0.6 g
Dye D'-9 0.02 g
Layer 15: Low blue-sensitive emulsion layer
Emulsion K' silver 0.2
g
Emulsion L' silver 0.2
g
Gelatin 0.9 g
Coupler C'-5 0.6 g
Additive F'-2 0.2 mg
Additive F'-5 0.4 mg
Addivive F'-8 0.05 mg
Layer 16: Medium blue-sensitive emulsion layer
Emulsion L' silver 0.1
g
Emulsion M' silver 0.4
g
Gelatin 0.7 g
Coupler C'-6 0.5 g
Additive F'-2 0.04 mg
Additive F'-8 0.04 mg
Layer 17: High blue-sensitive emulsion layer
Emulsion N' silver 0.4
g
Gelatin 0.7 g
Coupler C'-6 0.5 g
Additive F'-2 0.4 mg
Additive F'-8 0.02 mg
Additive F'-9 1.0 mg
Layer 18: First protective layer
Gelatin 0.9 g
UV absorbent U'-1 0.04 g
UV absorbent U'-2 0.01 g
UV absorbent U'-3 0.03 g
UV absorbent U'-4 0.03 g
UV absorbent U'-5 0.05 g
UV absorbent U'-6 0.05 g
Organic solvent having 0.02 g
a high-boiling point Oil-1
Formalin scavenger
Cpd-C 0.2 g
Cpd-I 0.4 g
Latex dispersion of 0.05 g
ethylacrylate
Dye D'-3 0.05 g
Additive Cpd-J 0.02 g
Additive F'-1 1.0 mg
Additive Cpd-N 0.01 g
Additive F'-6 1.0 mg
Additive F'-7 0.5 mg
Additive M-2 0.05 g
Layer 19: Second protective layer
Gelatin 0.7 g
Silver bromoiodide emulsion
0.1 g
(av. grain size: 0.06 .mu.m;
variation coefficient: 16%;
AgI content: 1.0 mol %)
Polymethylmethacrylate 0.1 g
(av. grain size: 1.5 .mu.m)
Copolymer (1:1) of methyl-
0.1 g
methacrylate and acrylic acid
(av. grain size: 1.5 .mu.m)
Silicone oil 0.03 g
Surfactant W'-1 3.0 mg
Surfactant W'-2 0.03 g
Layer 20: Back layer
Gelatin 10 g
UV absorbent U'-1 0.05 g
UV absorbent U'-2 0.02 g
Organic solvent having 0.01 g
a high-boiling point Oil-1
Layer 21: Back protective layer
Gelatin 5 g
Polymethylmethacrylate 0.03 g
(av. grain size: 1.5 .mu.m)
Copolymer (4:6) of methyl-
0.1 g
methacrylate and acrylic acid
(av. grain size: 1.5 .mu.m)
Surfactant W'-1 1 mg
Surfactant W'-2 10 mg
______________________________________
Additive F'-1 was added to each of the silver halide emulsion layers.
Further, gelatin hardener H-1, coating surfactants W'-3 and W'-4, and
emulsifying surfactant W'-5 or W'-6 were added to each layer.
Still further, phenol 1,2-benzisothiazoline-3-one, 2-phenoxyethanol, phenyl
isothiocyanate, and phenetyl alcohol were added as anticeptcs and
antifungal agents.
The structures of the compounds used in this example will be specified
below:
##STR25##
The silver bromoiodide emulsions used in Sample 310 are as follows:
______________________________________
Av. GS VC AgI C.
Emulsion
Features (.mu.m) (%) (%)
______________________________________
A' Monodispersed tetra-
0.35 16 4.5
decahedral grains
B' Monodispersed cubic,
0.45 10 5.0
internal latent
grains
C' Monodispersed tetra-
0.60 18 4.0
decahedral grains
D' Polydispersed twinned
1.10 25 3.0
grains having average
aspect ratio of 1.5
E' Monodispersed cubic
0.30 17 4.0
grains
F' Monodispersed cubic
0.40 16 4.0
grains
G' Monodispersed cubic,
0.50 11 4.5
internal latent
grains
H' Monodispersed tetra-
0.65 9 3.5
decahedral grains
I' Polydispersed twinned
1.20 28 3.0
grains having average
aspect ratio of 1.5
K' Monodispersed tetra-
0.60 17 2.0
decahedral grains
L' Monodispersed octa-
0.80 14 2.0
hedral grains
M' Monodispersed octa-
1.00 18 4.0
hedral grains
N' Polydispersed twinned
1.45 27 3.5
grains having average
aspect ratio of 1.5
______________________________________
Note:
"Av. GS," "VC," and "AgI C" stand for "average grain size," "variation
coefficient," and "AgI content," respectively.
Spectral Sensitization of Emulsions A' to N'
Sensitizing
Emulsion
Dyes Added Amount (g)*
Timing of Addition
______________________________________
A' S'-9 0.002 Right after chemical
sensitization
S'-1 0.125 Right after chemical
sensitization
S'-11 0.125 Right after chemical
sensitization
B' S'-1 0.01 Right after forming
grains
S'-2 0.25 Right after forming
grains
C' S'-1 0.02 Right after chemical
sensitization
S'-9 0.002 Right after chemical
sensitization
S'-2 0.25 Right after chemical
sensitization
D' S'-11 0.10 Right before chemical
sensitization
S'-2 0.01 Right before chemical
sensitization
S'-7 0.01 Right before chemical
sensitization
E' S'-3 0.5 Right after chemical
sensitization
S'-10 0.05 Right after chemical
sensitization
S'-4 0.1 Right after chemical
sensitization
F' S'-3 0.3 Right after chemical
sensitization
S'-4 0.1 Right after chemical
sensitization
G' S'-3 0.25 Right after forming
grains
S'-4 0.08 Right after forming
grains
H' S'-3 0.2 During the forming
of grains
S'-10 0.1 Right after chemical
sensitization
S'-4 0.06 During the forming
of grains
I' S'-3 0.3 Right before chemi-
cal sensitization
S'-4 0.07 Right before chemi-
cal sensitization
S'-8 0.1 Right before chemi-
cal sensitization
K' S'-5 0.2 During the forming
of grains
S'-6 0.05 During the forming
of grains
L' S'-5 0.22 Right after forming
grains
S'-6 0.06 Right after forming
grains
M' S'-5 0.15 Right after chemical
sensitization
S'-6 0.04 Right after chemical
sensitization
N' S'-5 0.22 Right after forming
grains
S'-6 0.06 Right after forming
grains
______________________________________
Note*:
amount used per mol of silver halide
Sample 302 was prepared in the same way as Sample 1, except that emulsion 1
was used in the layer 15 in place of emulsions K' and L', and in the layer
16 in place of emulsion L' in the same coating amount of silver.
Sample 303 was prepared in the same way as Sample 301, except that 0.007
g/m.sup.2 of SA-6 was added to the layers 17 and 18.
Samples 304 to 307 were prepared by the same method as Sample 303, except
that emulsions 1' to 4' were used respectively in the layer 15 in place of
emulsions K' and L' and in the layer 16 in place of emulsion L'.
Samples 301 to 307, thus prepared, were exposed for measuring their MTF
values, and then developed in the method specified below. Another set of
Samples 301 to 307 were bent by a predetermined angle and then developed,
thereby to determine the change in density of each sample due to the
pressure applied to it. The results were as is shown in the following
Table 7.
______________________________________
Processing Method
Process Time Temperature
______________________________________
First development
6 min. 38.degree. C.
Water washing 2 min. "
Reversing 2 min. "
Color development
6 min. "
Adjustment 2 min. "
Bleaching 6 min. "
Fixing 4 min. "
Water washing 4 min. "
Stabilization 1 min. Room temp.
Drying
______________________________________
The process solutions used in the above processing method had the
compositions specified below:
______________________________________
First Developing Solution
Water 700 ml
Nitrilo-N,N,N-trimethylene-
2 g
phosphonic acid-5-sodium salt
Sodium sulfite 30 g
Sodium 20 g
Hydroquinone monosulfonate
Potassium carbonate 33 g
1-phenyl-4-methyl-4- 2 g
hydroxymethyl-3-pyrazolidone
Potassium bromide 2.5 g
Potassium thiocyanate 1.2 g
Potassium iodide 2 mg
Water to make 1000 ml
Reversal solution
Water 700 ml
Nitrilo-N,N,N-trimethylene-
3 g
phosphonic acid-5-sodium salt
Stannous chloride (dihydrate)
1 g
P-aminophenol 0.1 g
Sodium hydroxide 8 g
Glacial acetic acid 15 ml
Water to make 1000 ml
Color developing solution
Water 700 ml
Nitrilo-N,N,N-trimethylene-
3 g
phosphonic acid-5-sodium salt
Sodium sulfite 7 g
Trisodium phosphate (dodecahydrate)
36 g
Potassium bromide 1 g
Potassium iodide 90 mg
Sodium hydroxide 3 g
Citrazinic acid 1.5 g
N-ethyl-N-.beta.-methane-
11 g
sulfonamidoethyl)-3-methyl-
4-aminoaniline sulfate
3,6-dithiaoctane-1,8-diol
1 g
Water to make 1000 ml
Adjusting water
Water 700 ml
Sodium sulfite 12 g
Sodium ethylenediamine- 8 g
tetraacetate (dihydrate)
Thioglycerin 0.4 ml
water to make 1000 ml
Bleaching Solution
Water 800 ml
Sodium ethylenediamine- 2 g
tetraacetate (dihydrate)
Ammonium ferric ethylenediamine
120 g
tetraacetate (dihydrate)
Potassium bromide 100 g
Ammonium nitrate 10 g
Water to make 1000 ml
Fixing Solution
Water 800 ml
Sodium thiosulfate 80.0 g
Sodium sulfite 5.0 g
Sodium bisulfite 5.0 g
Water to make 1000 ml
Stabilizing Solution
Water 800 ml
Formalin (37 wt %) 5.0 ml
Polyoxyethylene-p-mono- 0.5 ml
nonylphenyl ether (av.
polymerization degree: 10)
Water to make 1000 ml
______________________________________
The same results were obtained when the samples were washed with the
following washing solution, after they had been fixed.
______________________________________
Washing Solution
______________________________________
Disodium ethylenediamine 0.4 g
tetraacetate
Water to make 1000 ml
pH adjusted by sodium hydroxide
7.0
______________________________________
TABLE 7
__________________________________________________________________________
Compound in
Photographic Properties
Emulsion Layers MTF Pressure
Sample Layer 15
Layer 16
17 and 18
value 1)
Properties 2)
__________________________________________________________________________
301 (comp.)
K', L'
L', M'
-- 0.20 2
302 (comp.)
1' 1', M'
-- 0.23 1
303 (comp.)
K', L'
L', M'
SA-6 0.22 2
304 (Invention)
1' 1', M'
" 0.26 1
305 (Invention)
2' 2', M'
" 0.26 3
306 (Invention)
3' 3', M'
" 0.26 4
307 (Invention)
4' 4', M'
" 0.26 5
__________________________________________________________________________
1) Value for a magenta image at 60 cycles/mm
2) One of 5 levels, visually determined by the change in density due to
bend (5: best; 1: worst)
As is evident from Table 7, Samples 304 to 307, which were combination of
tabular emulsions 1' to 4' of the invention and the compounds of the
invention, excelled in sharpness represented by their MTF values. It is
also clear from Table 7 that emulsions 2' to 4', which contained grains
having many dislocation lines, helped to improve pressure resistance, and
that emulsions 3' and 4', which contained grains not differing much in
silver iodide content, helped to improve pressure resistance very much.
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